Organic electroluminescent materials and devices

ABSTRACT

A compound having a formula M(L A ) x (L B ) y (L C ) z , where ligand L A  is 
                         
ligand L B  is
 
                         
and ligand L C  is
 
                         
is disclosed. In formula M(L A ) x (L B ) y (L C ) z , M is a metal having an atomic number greater than 40; x is 1 or 2; y is 0, 1, or 2; z is 0, 1, or 2; x+y+z is the oxidation state of the metal M; A 1 -A 8  are carbon or nitrogen; ring B is bonded to ring A through a C—C bond; M is bonded to ring A through a M-C bond; X is O, S, Se, CRR′, or NR 1 ; rings C and D are each independently a 5 or 6-membered carbocyclic or heterocyclic ring; R 3  represents mono, or di-substitution, or no substitution; R 2 , R C , and R D  each independently represent mono, di, tri, or tetra-substitution, or no substitution; R 4  represents mono, di, tri, or tetra-substitution; at least one R 4  is a five-membered or six-membered heterocyclic ring which can be further substituted by R E ; where R E  represents mono, di, tri, or tetra-substitution, or no substitution; each R substituent is independently selected from a variety of moieties; and any adjacent R substitutents are optionally joined to form a ring.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation-in-part application of U.S.application Ser. No. 14/539,412, filed Nov. 12, 2014, the disclosure ofwhich is incorporated herein by reference in its entirety. Thisapplication also claims priority under 35 U.S.C. § 119(e) to U.S.Provisional Application Ser. No. 62/089,397, filed Dec. 9, 2014, thedisclosure of which is incorporated herein by reference in its entirety.

PARTIES TO A JOINT RESEARCH AGREEMENT

The claimed invention was made by, on behalf of, and/or in connectionwith one or more of the following parties to a joint universitycorporation research agreement: Regents of the University of Michigan,Princeton University, University of Southern California, and UniversalDisplay Corporation. The agreement was in effect on and before the datethe claimed invention was made, and the claimed invention was made as aresult of activities undertaken within the scope of the agreement.

FIELD OF THE INVENTION

The present invention relates to compounds for use as emitters anddevices, such as organic light emitting diodes, including the same.

BACKGROUND

Opto-electronic devices that make use of organic materials are becomingincreasingly desirable for a number of reasons. Many of the materialsused to make such devices are relatively inexpensive, so organicopto-electronic devices have the potential for cost advantages overinorganic devices. In addition, the inherent properties of organicmaterials, such as their flexibility, may make them well suited forparticular applications such as fabrication on a flexible substrate.Examples of organic opto-electronic devices include organic lightemitting devices (OLEDs), organic phototransistors, organic photovoltaiccells, and organic photodetectors. For OLEDs, the organic materials mayhave performance advantages over conventional materials. For example,the wavelength at which an organic emissive layer emits light maygenerally be readily tuned with appropriate dopants.

OLEDs make use of thin organic films that emit light when voltage isapplied across the device. OLEDs are becoming an increasinglyinteresting technology for use in applications such as flat paneldisplays, illumination, and backlighting. Several OLED materials andconfigurations are described in U.S. Pat. Nos. 5,844,363, 6,303,238, and5,707,745, which are incorporated herein by reference in their entirety.

One application for phosphorescent emissive molecules is a full colordisplay. Industry standards for such a display call for pixels adaptedto emit particular colors, referred to as “saturated” colors. Inparticular, these standards call for saturated red, green, and bluepixels. Color may be measured using CIE coordinates, which are wellknown to the art.

One example of a green emissive molecule is tris(2-phenylpyridine)iridium, denoted Ir(ppy)₃, which has the following structure:

In this, and later figures herein, we depict the dative bond fromnitrogen to metal (here, Ir) as a straight line.

As used herein, the term “organic” includes polymeric materials as wellas small molecule organic materials that may be used to fabricateorganic opto-electronic devices. “Small molecule” refers to any organicmaterial that is not a polymer, and “small molecules” may actually bequite large. Small molecules may include repeat units in somecircumstances. For example, using a long chain alkyl group as asubstituent does not remove a molecule from the “small molecule” class.Small molecules may also be incorporated into polymers, for example as apendent group on a polymer backbone or as a part of the backbone. Smallmolecules may also serve as the core moiety of a dendrimer, whichconsists of a series of chemical shells built on the core moiety. Thecore moiety of a dendrimer may be a fluorescent or phosphorescent smallmolecule emitter. A dendrimer may be a “small molecule,” and it isbelieved that all dendrimers currently used in the field of OLEDs aresmall molecules.

As used herein, “top” means furthest away from the substrate, while“bottom” means closest to the substrate. Where a first layer isdescribed as “disposed over” a second layer, the first layer is disposedfurther away from substrate. There may be other layers between the firstand second layer, unless it is specified that the first layer is “incontact with” the second layer. For example, a cathode may be describedas “disposed over” an anode, even though there are various organiclayers in between.

As used herein, “solution processible” means capable of being dissolved,dispersed, or transported in and/or deposited from a liquid medium,either in solution or suspension form.

A ligand may be referred to as “photoactive” when it is believed thatthe ligand directly contributes to the photoactive properties of anemissive material. A ligand may be referred to as “ancillary” when it isbelieved that the ligand does not contribute to the photoactiveproperties of an emissive material, although an ancillary ligand mayalter the properties of a photoactive ligand.

As used herein, and as would be generally understood by one skilled inthe art, a first “Highest Occupied Molecular Orbital” (HOMO) or “LowestUnoccupied Molecular Orbital” (LUMO) energy level is “greater than” or“higher than” a second HOMO or LUMO energy level if the first energylevel is closer to the vacuum energy level. Since ionization potentials(IP) are measured as a negative energy relative to a vacuum level, ahigher HOMO energy level corresponds to an IP having a smaller absolutevalue (an IP that is less negative). Similarly, a higher LUMO energylevel corresponds to an electron affinity (EA) having a smaller absolutevalue (an EA that is less negative). On a conventional energy leveldiagram, with the vacuum level at the top, the LUMO energy level of amaterial is higher than the HOMO energy level of the same material. A“higher” HOMO or LUMO energy level appears closer to the top of such adiagram than a “lower” HOMO or LUMO energy level.

As used herein, and as would be generally understood by one skilled inthe art, a first work function is “greater than” or “higher than” asecond work function if the first work function has a higher absolutevalue. Because work functions are generally measured as negative numbersrelative to vacuum level, this means that a “higher” work function ismore negative. On a conventional energy level diagram, with the vacuumlevel at the top, a “higher” work function is illustrated as furtheraway from the vacuum level in the downward direction. Thus, thedefinitions of HOMO and LUMO energy levels follow a different conventionthan work functions.

More details on OLEDs, and the definitions described above, can be foundin U.S. Pat. No. 7,279,704, which is incorporated herein by reference inits entirety.

SUMMARY OF THE INVENTION

According to one embodiment, a compound having a formulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z), where the ligand L_(A) is

the ligand L_(B) is

and the ligand L_(C) is

is provided. In the structure of formulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z):

M is a metal having an atomic number greater than 40;

x is 1, or 2;

y is 0, 1, or 2;

z is 0, 1, or 2;

x+y+z is the oxidation state of the metal M;

A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ are carbon or nitrogen;

ring B is bonded to ring A through a C—C bond;

M is bonded to ring A through a M-C bond;

X is selected from the group consisting of O, S, Se, CRR′, and NR¹;

rings C and D are each independently a 5 or 6-membered carbocyclic orheterocyclic ring;

R³ represents mono, or di-substitution, or no substitution;

R², R^(C), and R^(D) each independently represent mono, di, tri, ortetra-substitution, or no substitution;

R⁴ represents mono, di, tri, or tetra-substitution;

at least one R⁴ is a five-membered or six-membered heterocyclic ringwhich can be further substituted by R^(E);

R^(E) represents mono, di, tri, or tetra-substitution, or nosubstitution; each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D), R^(X), R^(Y),R^(Z) and R^(E) are independently selected from the group consisting ofhydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl,alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester,nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof; and any adjacent substitutents of R, R′, R¹, R²,R³, R⁴, R^(C), R^(D), R^(X), R^(Y), R^(Z) and R^(E) are optionallyjoined to form a ring.

In some embodiments of the compound, at least one R⁴ of the ligand L_(A)is a six-membered heterocyclic ring having at least two nitrogen atomswhere the only heteroatom is nitrogen, such as a triazine moiety.

According to another embodiment, a device comprising one or more organiclight emitting devices is also provided. At least one of the one or moreorganic light emitting devices can include an anode, a cathode, and anorganic layer, disposed between the anode and the cathode, wherein theorganic layer can include the compound of FormulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z). The device can be a consumerproduct, an electronic component module, an organic light-emittingdevice, and/or a lighting panel.

According to yet another embodiment, a formulation containing a compoundof Formula M(L_(A))_(x)(L_(B))_(y)(L_(C))_(z) is provided.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an organic light emitting device.

FIG. 2 shows an inverted organic light emitting device that does nothave a separate electron transport layer.

FIG. 3 shows ligand L_(A), ligand L_(B), and ligand L_(C) as describedherein.

DETAILED DESCRIPTION

Generally, an OLED comprises at least one organic layer disposed betweenand electrically connected to an anode and a cathode. When a current isapplied, the anode injects holes and the cathode injects electrons intothe organic layer(s). The injected holes and electrons each migratetoward the oppositely charged electrode. When an electron and holelocalize on the same molecule, an “exciton,” which is a localizedelectron-hole pair having an excited energy state, is formed. Light isemitted when the exciton relaxes via a photoemissive mechanism. In somecases, the exciton may be localized on an excimer or an exciplex.Non-radiative mechanisms, such as thermal relaxation, may also occur,but are generally considered undesirable.

The initial OLEDs used emissive molecules that emitted light from theirsinglet states (“fluorescence”) as disclosed, for example, in U.S. Pat.No. 4,769,292, which is incorporated by reference in its entirety.Fluorescent emission generally occurs in a time frame of less than 10nanoseconds.

More recently, OLEDs having emissive materials that emit light fromtriplet states (“phosphorescence”) have been demonstrated. Baldo et al.,“Highly Efficient Phosphorescent Emission from OrganicElectroluminescent Devices,” Nature, vol. 395, 151-154, 1998;(“Baldo-I”) and Baldo et al., “Very high-efficiency green organiclight-emitting devices based on electrophosphorescence,” Appl. Phys.Lett., vol. 75, No. 3, 4-6 (1999) (“Baldo-II”), which are incorporatedby reference in their entireties. Phosphorescence is described in moredetail in U.S. Pat. No. 7,279,704 at cols. 5-6, which are incorporatedby reference.

FIG. 1 shows an organic light emitting device 100. The figures are notnecessarily drawn to scale. Device 100 may include a substrate 110, ananode 115, a hole injection layer 120, a hole transport layer 125, anelectron blocking layer 130, an emissive layer 135, a hole blockinglayer 140, an electron transport layer 145, an electron injection layer150, a protective layer 155, a cathode 160, and a barrier layer 170.Cathode 160 is a compound cathode having a first conductive layer 162and a second conductive layer 164. Device 100 may be fabricated bydepositing the layers described, in order. The properties and functionsof these various layers, as well as example materials, are described inmore detail in U.S. Pat. No. 7,279,704 at cols. 6-10, which areincorporated by reference.

More examples for each of these layers are available. For example, aflexible and transparent substrate-anode combination is disclosed inU.S. Pat. No. 5,844,363, which is incorporated by reference in itsentirety. An example of a p-doped hole transport layer is m-MTDATA dopedwith F₄-TCNQ at a molar ratio of 50:1, as disclosed in U.S. PatentApplication Publication No. 2003/0230980, which is incorporated byreference in its entirety. Examples of emissive and host materials aredisclosed in U.S. Pat. No. 6,303,238 to Thompson et al., which isincorporated by reference in its entirety. An example of an n-dopedelectron transport layer is BPhen doped with Li at a molar ratio of 1:1,as disclosed in U.S. Patent Application Publication No. 2003/0230980,which is incorporated by reference in its entirety. U.S. Pat. Nos.5,703,436 and 5,707,745, which are incorporated by reference in theirentireties, disclose examples of cathodes including compound cathodeshaving a thin layer of metal such as Mg:Ag with an overlyingtransparent, electrically-conductive, sputter-deposited ITO layer. Thetheory and use of blocking layers is described in more detail in U.S.Pat. No. 6,097,147 and U.S. Patent Application Publication No.2003/0230980, which are incorporated by reference in their entireties.Examples of injection layers are provided in U.S. Patent ApplicationPublication No. 2004/0174116, which is incorporated by reference in itsentirety. A description of protective layers may be found in U.S. PatentApplication Publication No. 2004/0174116, which is incorporated byreference in its entirety.

FIG. 2 shows an inverted OLED 200. The device includes a substrate 210,a cathode 215, an emissive layer 220, a hole transport layer 225, and ananode 230. Device 200 may be fabricated by depositing the layersdescribed, in order. Because the most common OLED configuration has acathode disposed over the anode, and device 200 has cathode 215 disposedunder anode 230, device 200 may be referred to as an “inverted” OLED.Materials similar to those described with respect to device 100 may beused in the corresponding layers of device 200. FIG. 2 provides oneexample of how some layers may be omitted from the structure of device100.

The simple layered structure illustrated in FIGS. 1 and 2 is provided byway of non-limiting example, and it is understood that embodiments ofthe invention may be used in connection with a wide variety of otherstructures. The specific materials and structures described areexemplary in nature, and other materials and structures may be used.Functional OLEDs may be achieved by combining the various layersdescribed in different ways, or layers may be omitted entirely, based ondesign, performance, and cost factors. Other layers not specificallydescribed may also be included. Materials other than those specificallydescribed may be used. Although many of the examples provided hereindescribe various layers as comprising a single material, it isunderstood that combinations of materials, such as a mixture of host anddopant, or more generally a mixture, may be used. Also, the layers mayhave various sublayers. The names given to the various layers herein arenot intended to be strictly limiting. For example, in device 200, holetransport layer 225 transports holes and injects holes into emissivelayer 220, and may be described as a hole transport layer or a holeinjection layer. In one embodiment, an OLED may be described as havingan “organic layer” disposed between a cathode and an anode. This organiclayer may comprise a single layer, or may further comprise multiplelayers of different organic materials as described, for example, withrespect to FIGS. 1 and 2.

Structures and materials not specifically described may also be used,such as OLEDs comprised of polymeric materials (PLEDs) such as disclosedin U.S. Pat. No. 5,247,190 to Friend et al., which is incorporated byreference in its entirety. By way of further example, OLEDs having asingle organic layer may be used. OLEDs may be stacked, for example asdescribed in U.S. Pat. No. 5,707,745 to Forrest et al, which isincorporated by reference in its entirety. The OLED structure maydeviate from the simple layered structure illustrated in FIGS. 1 and 2.For example, the substrate may include an angled reflective surface toimprove out-coupling, such as a mesa structure as described in U.S. Pat.No. 6,091,195 to Forrest et al., and/or a pit structure as described inU.S. Pat. No. 5,834,893 to Bulovic et al., which are incorporated byreference in their entireties.

Unless otherwise specified, any of the layers of the various embodimentsmay be deposited by any suitable method. For the organic layers,preferred methods include thermal evaporation, ink-jet, such asdescribed in U.S. Pat. Nos. 6,013,982 and 6,087,196, which areincorporated by reference in their entireties, organic vapor phasedeposition (OVPD), such as described in U.S. Pat. No. 6,337,102 toForrest et al., which is incorporated by reference in its entirety, anddeposition by organic vapor jet printing (OVJP), such as described inU.S. Pat. No. 7,431,968, which is incorporated by reference in itsentirety. Other suitable deposition methods include spin coating andother solution based processes. Solution based processes are preferablycarried out in nitrogen or an inert atmosphere. For the other layers,preferred methods include thermal evaporation. Preferred patterningmethods include deposition through a mask, cold welding such asdescribed in U.S. Pat. Nos. 6,294,398 and 6,468,819, which areincorporated by reference in their entireties, and patterning associatedwith some of the deposition methods such as ink jet and OVJD. Othermethods may also be used. The materials to be deposited may be modifiedto make them compatible with a particular deposition method. Forexample, substituents such as alkyl and aryl groups, branched orunbranched, and preferably containing at least 3 carbons, may be used insmall molecules to enhance their ability to undergo solution processing.Substituents having 20 carbons or more may be used, and 3-20 carbons isa preferred range. Materials with asymmetric structures may have bettersolution processibility than those having symmetric structures, becauseasymmetric materials may have a lower tendency to recrystallize.Dendrimer substituents may be used to enhance the ability of smallmolecules to undergo solution processing.

Devices fabricated in accordance with embodiments of the presentinvention may further optionally comprise a barrier layer. One purposeof the barrier layer is to protect the electrodes and organic layersfrom damaging exposure to harmful species in the environment includingmoisture, vapor and/or gases, etc. The barrier layer may be depositedover, under or next to a substrate, an electrode, or over any otherparts of a device including an edge. The barrier layer may comprise asingle layer, or multiple layers. The barrier layer may be formed byvarious known chemical vapor deposition techniques and may includecompositions having a single phase as well as compositions havingmultiple phases. Any suitable material or combination of materials maybe used for the barrier layer. The barrier layer may incorporate aninorganic or an organic compound or both. The preferred barrier layercomprises a mixture of a polymeric material and a non-polymeric materialas described in U.S. Pat. No. 7,968,146, PCT Pat. Application Nos.PCT/US2007/023098 and PCT/US2009/042829, which are herein incorporatedby reference in their entireties. To be considered a “mixture”, theaforesaid polymeric and non-polymeric materials comprising the barrierlayer should be deposited under the same reaction conditions and/or atthe same time. The weight ratio of polymeric to non-polymeric materialmay be in the range of 95:5 to 5:95. The polymeric material and thenon-polymeric material may be created from the same precursor material.In one example, the mixture of a polymeric material and a non-polymericmaterial consists essentially of polymeric silicon and inorganicsilicon.

Devices fabricated in accordance with embodiments of the invention canbe incorporated into a wide variety of electronic component modules (orunits) that can be incorporated into a variety of electronic products orintermediate components. Examples of such electronic products orintermediate components include display screens, lighting devices suchas discrete light source devices or lighting panels, etc. that can beutilized by the end-user product manufacturers. Such electroniccomponent modules can optionally include the driving electronics and/orpower source(s). Devices fabricated in accordance with embodiments ofthe invention can be incorporated into a wide variety of consumerproducts that have one or more of the electronic component modules (orunits) incorporated therein. Such consumer products would include anykind of products that include one or more light source(s) and/or one ormore of some type of visual displays. Some examples of such consumerproducts include flat panel displays, computer monitors, medicalmonitors, televisions, billboards, lights for interior or exteriorillumination and/or signaling, heads-up displays, fully or partiallytransparent displays, flexible displays, laser printers, telephones,cell phones, tablets, phablets, personal digital assistants (PDAs),laptop computers, digital cameras, camcorders, viewfinders,micro-displays, 3-D displays, vehicles, a large area wall, theater orstadium screen, or a sign. Various control mechanisms may be used tocontrol devices fabricated in accordance with the present invention,including passive matrix and active matrix. Many of the devices areintended for use in a temperature range comfortable to humans, such as18 degrees C. to 30 degrees C., and more preferably at room temperature(20-25 degrees C.), but could be used outside this temperature range,for example, from −40 degree C. to +80 degree C.

The materials and structures described herein may have applications indevices other than OLEDs. For example, other optoelectronic devices suchas organic solar cells and organic photodetectors may employ thematerials and structures. More generally, organic devices, such asorganic transistors, may employ the materials and structures.

The term “halo,” “halogen,” or “halide” as used herein includesfluorine, chlorine, bromine, and iodine.

The term “alkyl” as used herein contemplates both straight and branchedchain alkyl radicals. Preferred alkyl groups are those containing fromone to fifteen carbon atoms and includes methyl, ethyl, propyl,isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, thealkyl group may be optionally substituted.

The term “cycloalkyl” as used herein contemplates cyclic alkyl radicals.Preferred cycloalkyl groups are those containing 3 to 7 carbon atoms andincludes cyclopropyl, cyclopentyl, cyclohexyl, and the like.Additionally, the cycloalkyl group may be optionally substituted.

The term “alkenyl” as used herein contemplates both straight andbranched chain alkene radicals. Preferred alkenyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkenyl groupmay be optionally substituted.

The term “alkynyl” as used herein contemplates both straight andbranched chain alkyne radicals. Preferred alkynyl groups are thosecontaining two to fifteen carbon atoms. Additionally, the alkynyl groupmay be optionally substituted.

The terms “aralkyl” or “arylalkyl” as used herein are usedinterchangeably and contemplate an alkyl group that has as a substituentan aromatic group. Additionally, the aralkyl group may be optionallysubstituted.

The term “heterocyclic group” as used herein contemplates aromatic andnon-aromatic cyclic radicals. Hetero-aromatic cyclic radicals also meansheteroaryl. Preferred hetero-non-aromatic cyclic groups are thosecontaining 3 or 7 ring atoms which includes at least one hetero atom,and includes cyclic amines such as morpholino, piperdino, pyrrolidino,and the like, and cyclic ethers, such as tetrahydrofuran,tetrahydropyran, and the like. Additionally, the heterocyclic group maybe optionally substituted.

The term “aryl” or “aromatic group” as used herein contemplatessingle-ring groups and polycyclic ring systems. The polycyclic rings mayhave two or more rings in which two carbons are common to two adjoiningrings (the rings are “fused”) wherein at least one of the rings isaromatic, e.g., the other rings can be cycloalkyls, cycloalkenyls, aryl,heterocycles, and/or heteroaryls. Additionally, the aryl group may beoptionally substituted.

The term “heteroaryl” as used herein contemplates single-ringhetero-aromatic groups that may include from one to three heteroatoms,for example, pyrrole, furan, thiophene, imidazole, oxazole, thiazole,triazole, pyrazole, pyridine, pyrazine and pyrimidine, and the like. Theterm heteroaryl also includes polycyclic hetero-aromatic systems havingtwo or more rings in which two atoms are common to two adjoining rings(the rings are “fused”) wherein at least one of the rings is aheteroaryl, e.g., the other rings can be cycloalkyls, cycloalkenyls,aryl, heterocycles, and/or heteroaryls. Additionally, the heteroarylgroup may be optionally substituted.

The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heterocyclic group,aryl, and heteroaryl may be optionally substituted with one or moresubstituents selected from the group consisting of hydrogen, deuterium,halogen, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy,amino, cyclic amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acid, ether,ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, andcombinations thereof.

As used herein, “substituted” indicates that a substituent other than His bonded to the relevant position, such as carbon. Thus, for example,where R¹ is mono-substituted, then one R¹ must be other than H.Similarly, where R¹ is di-substituted, then two of R¹ must be other thanH. Similarly, where R¹ is unsubstituted, R¹ is hydrogen for allavailable positions.

The “aza” designation in the fragments described herein, i.e.aza-dibenzofuran, aza-dibenzothiophene, etc. means that one or more ofthe C—H groups in the respective fragment can be replaced by a nitrogenatom, for example, and without any limitation, azatriphenyleneencompasses both dibenzo[f,h]quinoxaline and dibenzo[f,h]quinoline. Oneof ordinary skill in the art can readily envision other nitrogen analogsof the aza-derivatives described above, and all such analogs areintended to be encompassed by the terms as set forth herein.

It is to be understood that when a molecular fragment is described asbeing a substituent or otherwise attached to another moiety, its namemay be written as if it were a fragment (e.g. phenyl, phenylene,naphthyl, dibenzofuryl) or as if it were the whole molecule (e.g.benzene, naphthalene, dibenzofuran). As used herein, these differentways of designating a substituent or attached fragment are considered tobe equivalent.

According to one embodiment, a compound having a formulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z), where the ligand L_(A) is

the ligand L_(B) is

and the ligand L_(C) is

is disclosed. In the structure of formulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z):

M is a metal having an atomic number greater than 40;

x is 1, or 2;

y is 0, 1, or 2;

z is 0, 1, or 2;

x+y+z is the oxidation state of the metal M;

A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ are carbon or nitrogen;

ring B is bonded to ring A through a C—C bond;

M is bonded to ring A through a M-C bond;

X is selected from the group consisting of O, S, Se, CRR′, and NR¹;

rings C and D are each independently a 5 or 6-membered carbocyclic orheterocyclic ring;

R³ represents mono, or di-substitution, or no substitution;

R², R^(C), and R^(D) each independently represent mono, di, tri, ortetra-substitution, or no substitution;

R⁴ represents mono, di, tri, or tetra-substitution;

at least one R⁴ is a five-membered or six-membered heterocyclic ringwhich can be further substituted by R^(E);

R^(E) represents mono, di, tri, or tetra-substitution, or nosubstitution;

each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D), R^(X), R^(Y), R^(Z) andR^(E) are independently selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof; and

any adjacent substitutents of R, R′, R¹, R², R³, R⁴, R^(C), R^(D),R^(X), R^(Y), R^(Z) and R^(E) are optionally joined to form a ring.

As used herein, unless otherwise specified, the generalized structure ofLigand L_(A)

encompasses both instances where the heteroatom X of the polycyclicmoiety faces Ring B, and instances where the heteroatom X of thepolycyclic moiety faces away from Ring B, as shown in formula I

In some embodiments, M is selected from the group consisting of Ir, Rh,Re, Ru, Os, Pt, Au, and Cu. In some embodiments, M is Ir.

In some embodiments, the compound has the formula M(L_(A))₂(L_(C)). Insome embodiments, the compound has the formula M(L_(A))(L_(B))₂.

In some embodiments, A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ are carbon. Insome embodiments, exactly one of A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ isnitrogen. In some embodiments, exactly two of A¹, A², A³, A⁴, A⁵, A⁶,A⁷, and A⁸ are nitrogen. In some embodiments, exactly one of A⁵, A⁶, A⁷,and A⁸ is nitrogen, while A¹, A², A³, and A⁴ are carbon.

In some embodiments, X is O. In some embodiments, X is NR¹. In someembodiments, X is CRR′.

In some embodiments, R² is substituted at the A⁷ position. In someembodiments, at least one R⁴ is a five-membered or six-membered aromaticheterocyclic ring. In some embodiments, exactly one R⁴ is afive-membered or six-membered aromatic heterocyclic ring.

In some embodiments, at least one R⁴ is a six-membered aromaticheterocyclic ring where the only heteroatom is nitrogen. In someembodiments, exactly one R⁴ is a six-membered aromatic heterocyclic ringwhere the only heteroatom is nitrogen. In some embodiments, there is atleast one R⁴ or exactly one R⁴ that is a six-membered aromaticheterocyclic ring, where the only heteroatom is nitrogen, and wherethere are one or two nitrogen atoms.

In some embodiments, at least one R⁴ is pyridine. In some embodiments,exactly one R⁴ is pyridine. In some embodiments, R4 is a pyridine thatis attached meta to the N-M bond of ring B.

In some embodiments, the exactly one R⁴ or at least one R⁴ is pyridinethat is substituted by alkyl. In some embodiments, the exactly one R⁴ orat least one R⁴ is pyridine that is substituted by alkyl at a positionortho to the N of the pyridine.

In some embodiments, L_(B) has the formula

where R⁵, R⁶, R⁷, and R⁸ are independently selected from groupconsisting of alkyl, cycloalkyl, aryl, and heteroaryl; and where atleast one of R⁵, R⁶, R⁷, and R⁸ has at least two C atoms. In someembodiments, R⁹ is hydrogen.

In some embodiments, each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D), R^(X),R^(Y), R^(Z) and R^(E) is independently selected from group consistingof hydrogen, deuterium, alkyl, cycloalkyl, and combinations thereof. Insome embodiments, each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D), R^(X),R^(Y), R^(Z) and R^(E) is independently selected from the groupconsisting of hydrogen, deuterium, methyl, ethyl, propyl, 1-methylethyl,butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, cyclobutyl, cyclopentyl, cyclohexyl, andcombinations thereof.

In some embodiments, ring C is benzene, and ring D is pyridine.

In some embodiments, L_(A) is selected from the group consisting of:

In some more specific embodiments, L_(A) is selected from the groupconsisting of:

L_(A1) through L_(A8), each L_(A9) through L_(A16), each represented bythe formula: represented by the formula:

  wherein in L_(A1): R¹ = R^(A1) and R² = R^(B1), in L_(A2): R¹ = R^(A2)and R² = R^(B1), in L_(A3): R¹ = R^(A3), R² = R^(B1), in L_(A4): R¹ =R^(A4), R² = R^(B1), in L_(A5): R¹ = R^(A1), R² = R^(B2), in L_(A6): R¹= R^(A2), R² = R^(B2), in L_(A7): R¹ = R^(A3), R² = R^(B2), and inL_(A8): R¹ = R^(A4), R² = R^(B2),,

  wherein in L_(A9): R¹ = R^(A1), R² = R^(B1), in L_(A10): R¹ = R^(A2),R² = R^(B1), in L_(A11): R¹ = R^(A3), R² = R^(B1), in L_(A12): R¹ =R^(A4), R² = R^(B1), in L_(A13): R¹ = R^(A1), R² = R^(B2), in L_(A14):R¹ = R^(A2), R² = R^(B2), in L_(A15): R¹ = R^(A3), R² = R^(B2), and inL_(A16): R¹ = R^(A4), R² = R^(B2),, L_(A17) through L_(A24), eachL_(A25) through L_(A32), each represented by the formula: represented bythe formula:

  wherein L_(A17):R¹ = R^(A1), R² = R^(B1), in L_(A18):R¹ =R^(A2), R²=R^(B1), in L_(A19):R¹ =R^(A3), R² =R^(B1), in L_(A20):R¹ =R^(A4), R²=R^(B1), in L_(A21):R¹ =R^(A1), R² =R^(B2), in L_(A22):R¹ =R^(A2), R²=R^(B2), in L_(A23):R¹ =R^(A3), R² =R^(B2), and in L_(A24):R¹ =R^(A4),R² =R^(B2),,

  wherein in L_(A25): R¹ = R^(A1), R² = R^(B1), in L_(A26): R¹ = R^(A2),R² = R^(B1), in L_(A27): R¹ = R^(A3), R² = R^(B1), in L_(A28): R¹ =R^(A4), R² = R^(B1), in L_(A29): R¹ = R^(A1), R² = R^(B2), in L_(A30):R¹ = R^(A2), R² = R^(B2), in L_(A31): R¹ = R^(A3), R² = R^(B2), and inL_(A32): R¹ = R^(A4), R² = R^(B2),, L_(A33) through L_(A40), eachL_(A41) through L_(A48), each represented by the formula: represented bythe formula:

  wherein in L_(A33): R¹ = R^(A1), R² = R^(B1), in L_(A34): R¹ = R^(A2),R² = R^(B1), in L_(A35): R¹ = R^(A3), R² = R^(B1), in L_(A36): R¹ =R^(A4), R² = R^(B1), in L_(A37): R¹ = R^(A1), R² = R^(B2), in L_(A38):R¹ = R^(A2), R² = R^(B2), in L_(A39): R¹ = R^(A3), R² = R^(B2), and inL_(A40): R¹ = R^(A4), R² = R^(B2),,

  where in L_(A41): R¹ = R^(A1), R² = R^(B1), in L_(A42): R¹ = R^(A2),R² = R^(B1), in L_(A43): R¹ = R^(A3), R² = R^(B1), in L_(A44): R¹ =R^(A4), R² = R^(B1), in L_(A45): R¹ = R^(A1), R² = R^(B2), in L_(A46):R¹ = R^(A2), R² = R^(B2), in L_(A47): R¹ = R^(A3), R² = R^(B2), and inL_(A48): R¹ = R^(A4), R² = R^(B2),, L_(A49) through L_(A56), eachL_(A57) through L_(A64), each L_(A65) through L_(A72), each representedby the formula: represented by the formula: represented by the formula:

  wherein in L_(A49): R¹ = R^(A1), R² = R^(B1), in L_(A50): R¹ = R^(A2),R² = R^(B1), in L_(A51): R¹ = R^(A3), R² = R^(B1), in L_(A52): R¹ =R^(A4), R² = R^(B1), in L_(A53): R¹ = R^(A1), R² = R^(B2), in L_(A54):R¹ = R^(A2), R² = R^(B2), in L_(A55): R¹ = R^(A3), R² = R^(B2), and inL_(A56): R¹ = R^(A4), R² = R^(B2),,

  where in L_(A57): R¹ = R^(A1), R² = R^(B1), in L_(A58): R¹ = R^(A2),R² = R^(B1), in L_(A59): R¹ = R^(A3), R² = R^(B1), in L_(A60): R¹ =R^(A4), R² = R^(B1), in L_(A61): R¹ = R^(A1), R² = R^(B2), in L_(A62):R¹ = R^(A2), R² = R^(B2), in L_(A63): R¹ = R^(A3), R² = R^(B2), and inL_(A64): R¹ = R^(A4), R² = R^(B2),,

  wherein in L_(A65): R¹ = R^(A1), R² = R^(B1), in L_(A66): R¹ = R^(A2),R² = R^(B1), in L_(A67): R¹ = R^(A3), R² = R^(B1), in L_(A68): R¹ =R^(A4), R² = R^(B1), in L_(A69): R¹ = R^(A1), R² = R^(B2), in L_(A70):R¹ = R^(A2), R² = R^(B2), in L_(A71): R¹ = R^(A3), R² = R^(B2), and inL_(A72): R¹ = R^(A4), R² = R^(B2),, L_(A73) through L_(A80), eachL_(A81) through L_(A88), each represented by the formula: represented bythe formula:

  wherein in L_(A73): R¹ = R^(A1), R² = R^(B1), in L_(A74): R¹ = R^(A2),R² = R^(B1), in L_(A75): R¹ = R^(A3), R² = R^(B1), in L_(A76): R¹ =R^(A3), R² = R^(B1), in L_(A77): R¹ = R^(A1), R² = R^(B2), in L_(A78):R¹ = R^(A2), R² = R^(B2), in L_(A79): R¹ = R^(A3), R² = R^(B2), and inL_(A80): R¹ = R^(A4), R² = R^(B2),,

  wherein in L_(A81): R¹ = R^(A1), R² = R^(B1), in L_(A82): R¹ = R^(A2),R² = R^(B1), in L_(A83): R¹ = R^(A3), R² = R^(B1), in L_(A84): R¹ =R^(A4), R² = R^(B1), in L_(A85): R¹ = R^(A1), R² = R^(B2), in L_(A86):R¹ = R^(A1), R² = R^(B2), in L_(A87): R¹ = R^(A3), R² = R^(B2), and inL_(A88): R¹ = R^(A4), R² = R^(B2),, L_(A89) through L_(A96), eachL_(A97) through L_(A100), each represented by the formula: representedby the formula:

  wherein in L_(A89): R¹ = R^(A1), R² = R^(B1), in L_(A90): R¹ = R^(A2),R² = R^(B1), in L_(A91): R¹ = R^(A3), R² = R^(B1), in L_(A92): R¹ =R^(A4), R² = R^(B1), in L_(A93): R¹ = R^(A1), R² = R^(B2), in L_(A94):R¹ = R^(A2), R² = R^(B2), in L_(A95): R¹ = R^(A3), R² = R^(B2), and inL_(A96): R¹ = R^(A4), R² = R^(B2),,

  where in L_(A97): X=O, R² = R^(B1), in L_(A98): X=O, R² = R^(B2), inL_(A99): X=S, R² = R^(B1), and in L_(A100): X=S, R² = R^(B2)., L_(A101)through L_(A104), each L_(A105) through L_(A110), each represented bythe formula: represented by the formula:

  wherein in L_(A101): X=O, R² = R^(B1), in L_(A102): X=O, R² = R^(B2),in L_(A103): X=S, R² = R^(B1), and in L_(A104): X=S, R² = R^(B2).,

  wherein in L_(A105): X=O, R² = R^(B1), in L_(A106): X=O, R² = R^(B2),in L_(A107): X=S, R² = R^(B1), in L_(A108): X=S, R² = R^(B2), inL_(A109): X=C(CH₃)₂, R² = R^(B1), and in L_(A110): X=C(CH₃)₂, R² =R^(B2)., L_(A111) through L_(A116), each L_(A117) through L_(A122), eachL_(A123) through L_(A128), each represented by the formula: representedby the formula: represented by the formula:

  wherein in L_(A111): X=O, R² = R^(B1), in L_(A112): X=O, R² = R^(B2),in L_(A113): X=S, R² = R^(B1), in L_(A114): X=S, R² = R^(B2), inL_(A115): X=C(CH₃)₂, R² = R^(B1), and in L_(A116): X=C(CH₃)₂, R² =R^(B2).,

  wherein in L_(A117): X=O, R² = R^(B1), in L_(A118): X=O, R² = R^(B2),in L_(A119): X=S, R² = R^(B1), in L_(A120): X=S, R² = R^(B2), inL_(A121): X=C(CH₃)₂, R² = R^(B1), and in L_(A122): X=C(CH₃)₂, R² =R^(B2).,

  wherein in L_(A123): X=O, R² = R^(B1), in L_(A124): X=O, R² = R^(B2),in L_(A125): X=S, R² = R^(B1), in L_(A126): X=S, R² = R^(B2), inL_(A127): X=C(CH₃)₂, R² = R^(B1), and in L_(A128): X=C(CH₃)₂, R² =R^(B2)., L_(A129) through L_(A134), each L_(A135) through L_(A140), eachL_(A141) through L_(A146), each represented by the formula: representedby the formula: represented by the formula:

  wherein in L_(A129): X=O, R² = R^(B1), in L_(A130): X=O, R² = R^(B2),in L_(A131): X=S, R² = R^(B1), in L_(A132): X=S, R² = R^(B2), inL_(A133): X=C(CH₃)₂, R² = R^(B1), and in L_(A134): X=C(CH₃)₂, R² =R^(B2).,

  wherein in L_(A135): X=O, R² = R^(B1), in L_(A136): X=O, R² = R^(B2),in L_(A137): X=S, R² = R^(B1), in L_(A138): X=S, R² = R^(B2), inL_(A139): X=C(CH₃)₂, R² = R^(B1), and in L_(A140): X=C(CH₃)₂, R² =R^(B2).,

  wherein in L_(A141): X=O,R² = R^(B1), in L_(A142): X=O, R² = R^(B2),in L_(A143): X=S, R² = R^(B1), in L_(A144): X=S, R² = R^(B2), inL_(A145): X=C(CH₃)₂, R² = R^(B1), and L_(A146): X=C(CH₃)₂, R² = R^(B2).,L_(A147) through L_(A152), each L_(A153) through L_(A158), each L_(A159)through L_(A164), each represented by the formula: represented by theformula: represented by the formula:

  wherein in L_(A147): R¹ = R^(A1), R² = R^(B1), in L_(A148): R¹ =R^(A2), R² = R^(B1), in L_(A149)R¹ = R^(A1), R² = R^(B2), in L_(A150):R¹ = R^(A2), R² = R^(B2), in L_(A151): X=C(CH₃)₂, R² = R^(B1), and inL_(A152): X=C(CH₃)₂, R² = R^(B2).,

  wherein in L_(A153): R¹ = R^(A1), R² = R^(B1), in L_(A154): R¹=R^(A2), R² = R^(B1), in L_(A155): R¹ =R^(A1), R² = R^(B2), in L_(A156):R¹ =R^(A2), R² = R^(B2), in L_(A157): X=C(CH₃)₂, R² = R^(B1), and inL_(A158): X=C(CH₃)₂, R² = R^(B2).,

  wherein in L_(A159): X=O, R² = R^(B1), in L_(A160): X=O, R² = R^(B2),in L_(A161): X=S, R² = R^(B1), in L_(A162): X=S, R² = R^(B2), inL_(A163): X=C(CH₃)₂, R² = R^(B1), and in L_(A164): X=C(CH₃)₂, R² =R^(B2)., L_(A165) through L_(A170), each L_(A171) through L_(A176), eachrepresented by the formula: represented by the formula:

  wherein in L_(A165): X=O, R² = R^(B1), in L_(A166): X=O, R² = R^(B2),in L_(A167): X=S, R² = R^(B1), in L_(A168): X=S, R² = R^(B2), inL_(A169): X=C(CH₃)₂, R² = R^(B1), and in L_(A170): X=C(CH₃)₂, R² =R^(B2).,

  wherein in L_(A171): X=O, R² = R^(B1), in L_(A172): X=O, R² = R^(B2),in L_(A173): X=S, R² = R^(B1), in L_(A174): X=S, R² = R^(B2), L_(A175):X=C(CH₃)₂, R² = R^(B1), and L_(A176): X=C(CH₃)₂, R² = R^(B2)., andL_(A177) through L_(A182), each represented by the formula:

  wherein in L_(A177): X=O, R² = R^(B1), in L_(A178): X=O, R² = R^(B2),in L_(A179): X=S, R² = R^(B1), in L_(A180): X=S, R² = R^(B2), inL_(A181): X=C(CH₃)₂, R² = R^(B1), and in L_(A182): X=C(CH₃)₂, R² =R^(B2)..In the structures of L_(A1) through L_(A182), R^(A1) to R^(A4) have the

following structures: R^(A1), R^(A2), R^(A3), and R^(A4), and R^(B1) andR^(B2) have the following

structures: R^(B1), and R^(B2).

In some embodiments, L_(B) is selected from the group consisting of:

In some embodiments, L_(C) is selected from the group consisting of:

In some embodiments, the compound can be an emissive dopant. In someembodiments, the compound can produce emissions via phosphorescence,fluorescence, thermally activated delayed fluorescence, i.e., TADF (alsoreferred to as E-type delayed fluorescence), triplet-tripletannihilation, or combinations of these processes.

In one embodiment of the compound, at least one R⁴ in the ligand L_(A)is a six-membered aromatic heterocyclic ring, such as a substitutedtriazine moiety, having at least two nitrogen atoms where the onlyheteroatom is nitrogen. The substitution can be at different positionsof the triazine and the side chains on the triazine can also bemodified. This embodiment will be hereinafter referred to as the“Triazine” embodiment. The triazine unit is a well-known electrondeficient building block and it should lower the LUMO energy level whichwill help make the compound function as a red emitter in an OLED.

The present disclosure encompasses the following further embodiments.The Triazine embodiment, wherein M is selected from the group consistingof Ir, Rh, Re, Ru, Os, Pt, Au, and Cu. A Triazine embodiment wherein Mis Ir. The Triazine embodiment wherein the compound has the formulaM(L_(A))₂(L_(C)). The Triazine embodiment wherein the compound has theformula M(L_(A))(L_(B))₂. A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ are carbon.The Triazine embodiment wherein exactly one of A¹, A², A³, A⁴, A⁵, A⁶,A⁷, and A⁸ is nitrogen. The Triazine embodiment wherein exactly one ofA⁵, A⁶, A⁷, and A⁸ is nitrogen, while A¹, A², A³, and A⁴ are carbon. TheTriazine embodiment wherein X is O. The Triazine embodiment wherein X isNR¹. The Triazine embodiment wherein at least one R⁴ is a six-memberedaromatic heterocyclic ring having two nitrogen atoms. The Triazineembodiment wherein at least one R⁴ is a six-membered aromaticheterocyclic ring having three nitrogen atoms. The Triazine embodimentwherein at least one R⁴ is selected from the group consisting oftriazine, pyrazine, pyrimidine, and pyridazine. The Triazine embodimentwherein L_(c) has the formula:

wherein R⁵, R⁶, R⁷, and R⁸ are independently selected from groupconsisting of alkyl, cycloalkyl, aryl, and heteroaryl,

wherein at least one of R⁵, R⁶, R⁷, and R⁸ has at least two C atoms. TheTriazine embodiment wherein each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D),R^(X), R^(Y), R^(Z) and R^(E) is independently selected from groupconsisting of hydrogen, deuterium, alkyl, cycloalkyl, and combinationsthereof. The Triazine embodiment wherein R⁹ is hydrogen. The Triazineembodiment wherein each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D), R^(X),R^(Y), R^(Z) and R^(E) is independently selected from the groupconsisting of hydrogen, deuterium, methyl, ethyl, propyl, 1-methylethyl,butyl, 1-methylpropyl, 2-methylpropyl, pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl,2,2-dimethylpropyl, cyclobutyl, cyclopentyl, cyclohexyl, andcombinations thereof. The Triazine embodiment wherein ring C is benzene,and ring D is pyridine. The Triazine embodiment wherein L_(A) isselected from the group consisting of:

The Triazine embodiment wherein L_(A) is selected from the groupconsisting of:

L_(A183) through L_(A198), each L_(A199) through L_(A214), eachrepresented by the formula: represented by the formula:

  wherein in L_(A183): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A184):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A185): X=O, R^(E) = R^(A5), R² =R^(B1), in L_(A186): X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A187): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A188): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A189): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A190): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A191): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A192): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A193): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A194): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A195): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A196): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A197): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A198): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A199): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A200):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A201): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A202): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A203): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A204): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A205): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A206): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A207): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A208): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A209): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A210): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A211): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A212): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A213): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A214): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A25)through L_(A230), each L_(A231) through L_(A246), each represented bythe formula: represented by the formula:

  wherein in L_(A215): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A216):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A217): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A218): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A219): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A220): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A221): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A222): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A223): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A224): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A225): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A226): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A227): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A228): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A229): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A230): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A231): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A232):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A233): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A234): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A235): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A236): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A237): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A238): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A239): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A240): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A241): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A242): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A243): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A244): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A245): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A246): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A247)through L_(A262), each L_(A263) through L_(A278), each represented bythe formula: represented by the formula:

  wherein in L_(A247): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A248):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A249): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A250): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A251): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A252): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A253): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A254): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A255): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A256): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A257): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A258): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A259): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A260): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A261): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A262): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A263): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A264):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A265): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A266): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A267): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A268): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A269): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A270): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A271): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A272): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A273): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A274): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A275): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A276): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A277): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A278): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A279)through L_(A294), each L_(A295) through L_(A310), each represented bythe formula: represented by the formula:

  wherein in L_(A279): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A280):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A281): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A282): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A283): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A284): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A285): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A286): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A287): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A288): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A289): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A290): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A291): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A292): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A293): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A294): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A295): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A296):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A297): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A298): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A299): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A300): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A301): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A302): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A303): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A304): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A305): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A306): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A307): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A308): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A309): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A310): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A311)through L_(A326), each L_(A327) through L_(A342), each represented bythe formula: represented by the formula:

  wherein in L_(A311):R^(E) = R^(A5), R² = R^(B1), R¹ = R^(C1), inL_(A312):R^(E) = R^(A5), R² = R^(B2), R¹ = R^(C1), in L_(A313):R^(E) =R^(A6), R² = R^(B1), R¹ = R^(C1), in L_(A314):R^(E) = R^(A6), R² =R^(B2), R¹ = R^(C1), in L_(A315):R^(E) = R^(A7), R² = R^(B1), R¹ =R^(C1), in L_(A316):R^(E) = R^(A7), R² = R^(B2), R¹ = R^(C1), inL_(A317):R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C1), in L_(A318):R^(E) =R^(A8), R² = R^(B2), R¹ = R^(C1), in L_(A319):R^(E) = R^(A5), R² =R^(B1), R¹ = R^(C2), in L_(A320):R^(E) = R^(A5), R² = R^(B2), R¹ =R^(C2), in L_(A321):R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), inL_(A322):R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A323):R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C2), in L_(A324):R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C2), in L_(A325):R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C2), and in L_(A326):R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2).,

  wherein in L_(A327):R^(E) = R^(A5), R² = R^(B1), R¹ = R^(C1), inL_(A328):R^(E) = R^(A5), R² = R^(B2), R¹ = R^(C1), in L_(A329):R^(E) =R^(A6), R² = R^(B1), R¹ = R^(C1), in L_(A330):R^(E) = R^(A6), R² =R^(B2), R¹ = R^(C1), in L_(A331):R^(E) = R^(A7), R² = R^(B1), R¹ =R^(C1), in L_(A332):R^(E) = R^(A7), R² = R^(B2), R¹ = R^(C1), inL_(A333):R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C1), in L_(A334):R^(E) =R^(A8), R² = R^(B2), R¹ = R^(C1), in L_(A335):R^(E) = R^(A5), R² =R^(B1), R¹ = R^(C2), in L_(A336):R^(E) = R^(A5), R² = R^(B2), R¹ =R^(C2), in L_(A337):R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), inL_(A338):R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A339):R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C2), in L_(A340):R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C2), in L_(A341):R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C2), and in L_(A342):R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2).,L_(A343) through L_(A358), each L_(A359) through L_(A374), eachrepresented by the formula: represented by the formula:

  wherein in L_(A343): R^(E) = R^(A5), R² = R^(B1), R¹ = R^(C1), inL_(A344): R^(E) = R^(A5), R² = R^(B2), R¹ = R^(C1), in L_(A345): R^(E) =R^(A6), R² = R^(B1), R¹ = R^(C1), in L_(A346): R^(E) = R^(A6), R² =R^(B2), R¹ = R^(C1), in L_(A347): R^(E) = R^(A7), R² = R^(B1), R¹ =R^(C1), in L_(A348): R^(E) = R^(A7), R² = R^(B2), R¹ = R^(C1), inL_(A349): R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C1), in L_(A350): R^(E) =R^(A8), R² = R^(B2), R¹ = R^(C1), in L_(A351): R^(E) = R^(A5), R² =R^(B1), R¹ = R^(C2), in L_(A352): R^(E) = R^(A5), R² = R^(B2), R¹ =R^(C2), in L_(A353): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), inL_(A354): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A355): R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C2), in L_(A356): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C2), in L_(A357): R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C2), and in L_(A358): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2).,

  wherein in L_(A359): R^(E) = R^(A5), R² = R^(B1), R¹ = R^(C1), inL_(A360): R^(E) = R^(A5), R² = R^(B2), R¹ = R^(C1), in L_(A361): R^(E) =R^(A6), R² = R^(B1), R¹ = R^(C1), in L_(A362): R^(E) = R^(A6), R² =R^(B2), R¹ = R^(C1), in L_(A363): R^(E) = R^(A7), R² = R^(B1), R¹ =R^(C1), in L_(A364): R^(E) = R^(A7), R² = R^(B2), R¹ = R^(C1), inL_(A365): R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C1), in L_(A366): R^(E) =R^(A8), R² = R^(B2), R¹ = R^(C1), in L_(A367): R^(E) = R^(A5), R² =R^(B1), R¹ = R^(C2), in L_(A368): R^(E) = R^(A5), R² = R^(B2), R¹ =R^(C2), in L_(A369): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), inL_(A370): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A371): R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C2), in L_(A372): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C2), in L_(A373): R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C2), and in L_(A374): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2).,L_(A375) through L_(A382), each L_(A383) through L_(A390), eachrepresented by the formula: represented by the formula:

  wherein in L_(A375): X=O, R^(E) = R^(A5), in L_(A376): X=O, R^(E) =R^(A6), in L_(A377): X=O, R^(E) = R^(A7), in L_(A378): X=O, R^(E) =R^(A8), in L_(A379): X=S, R^(E) = R^(A5), in L_(A380): X=S, R^(E) =R^(A5), in L_(A381): X=S, R^(E) = R^(A7), and in L_(A382): X=S, R^(E) =R^(A8).,

  wherein in L_(A383): X=O, R^(E) = R^(A5), in L_(A384): X=O, R^(E) =R^(A6), in L_(A385): X=O, R^(E) = R^(A7), in L_(A386): X=O, R^(E) =R^(A8), in L_(A387): X=S, R^(E) = R^(A5), in L_(A388): X=S, R^(E) =R^(A5), in L_(A389): X=S, R^(E) = R^(A7), and in L_(A390): X=S, R^(E) =R^(A8)., L_(A391) through L_(A406), each L_(A407) through L_(A422), eachrepresented by the formula: represented by the formula:

  wherein in L_(A391): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A392):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A393): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A394): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A395): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A396): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A397): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A398): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A399): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A400): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A401): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A402): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A403): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A404): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A405): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A406): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A407): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A408):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A409): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A410): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A411): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A412): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A413): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A414): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A415): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A416): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A417): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A418): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A419): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A420): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A421): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A422): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A423)through L_(A438), each L_(A439) through L_(A454), each represented bythe formula: represented by the formula:

  wherein in L_(A423): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A424):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A425): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A426): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A427): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A428): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A429): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A430): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A431): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A432): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A433): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A434): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A435): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A436): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A437): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A438): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A439): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A440):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A441): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A442): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A443): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A444): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A445): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A446): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A447): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A448): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A449): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A450): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A451): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A452): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A453): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A454): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A455)through L_(A462), each L_(A463) through L_(A470), each represented bythe formula: represented by the formula:

  wherein in L_(A455): X=O, R^(E) = R^(A5), in L_(A456): X=O, R^(E) =R^(A6), in L_(A457): X=O, R^(E) = R^(A7), in L_(A458): X=O, R^(E) =R^(A8), in L_(A459): X=S, R^(E) = R^(A5), in L_(A460): X=S, R^(E) =R^(A6), in L_(A461): X=S, R^(E) = R^(A7), and in L_(A462): X=S, R^(E) =R^(A8).

  wherein in L_(A463): X=O, R^(E) = R^(A5), in L_(A464): X=O, R^(E) =R^(A6), in L_(A465): X=O, R^(E) = R^(A7), in L_(A466): X=O, R^(E) =R^(A8), in L_(A467): X=S, R^(E) = R^(A5), in L_(A468): X=S, R^(E) =R^(A6), in L_(A469): X=S, R^(E) = R^(A7), and in L_(A470): X=S, R^(E) =R^(A8)., L_(A471) through L_(A478), each L_(A479) through L_(A486), eachrepresented by the formula: represented by the formula:

  wherein in L_(A471): R^(E) = R^(A5), R¹ = R^(C1), in L_(A472): R^(E) =R^(A6), R¹ = R^(C1), in L_(A473): R^(E) = R^(A7), R¹ = R^(C1), inL_(A474): R^(E) = R^(A8), R¹ = R^(C1), in L_(A475): R^(E) = R^(A5), R¹ =R^(C2), in L_(A476): R^(E) = R^(A6), R¹ = R^(C2), in L_(A477): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A478): R^(E) = R^(A8), R¹ = R^(C2).

  wherein in L_(A463): R^(E) = R^(A5), R¹ = R^(C1), in L_(A464): R^(E) =R^(A6), R¹ = R^(C1), in L_(A465): R^(E) = R^(A7), R¹ = R^(C1), inL_(A466): R^(E) = R^(A8), R¹ = R^(C1), in L_(A467): R^(E) = R^(A5), R¹ =R^(C2), in L_(A468): R^(E) = R^(A6), R¹ = R^(C2), in L_(A469): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A470): R^(E) = R^(A8), R¹ = R^(C2).,L_(A487) through L_(A494), each L_(A495) through L_(A502), eachrepresented by the formula: represented by the formula:

  wherein in L_(A487): R^(E) = R^(A5), R¹ = R^(C1), in L_(A488): R^(E) =R^(A6), R¹ = R^(C1), in L_(A489): R^(E) = R^(A7), R¹ = R^(C1), inL_(A490): R^(E) = R^(A8), R¹ = R^(C1), in L_(A491): R^(E) = R^(A5), R¹ =R^(C2), in L_(A492): R^(E) = R^(A6), R¹ = R^(C2), in L_(A493): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A494): R^(E) = R^(A8), R¹ = R^(C2).

  wherein in L_(A495): R^(E) = R^(A5), R¹ = R^(C1), in L_(A496): R^(E) =R^(A6), R¹ = R^(C1), in L_(A497): R^(E) = R^(A7), R¹ = R^(C1), inL_(A498): R^(E) = R^(A8), R¹ = R^(C1), in L_(A499): R^(E) = R^(A5), R¹ =R^(C2), in L_(A500): R^(E) = R^(A6), R¹ = R^(C2), in L_(A501): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A502): R^(E) = R^(A8), R¹ = R^(C2).,L_(A503) through L_(A518), each L_(A519) through L_(A534), eachrepresented by the formula: represented by the formula:

  wherein in L_(A503): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A504):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A505): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A506): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A507): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A508): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A509): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A510): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A511): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A512): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A513): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A514): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A515): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A516): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A517): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A518): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A519): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A520):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A521): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A522): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A523): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A524): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A525): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A526): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A527): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A528): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A529): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A530): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A531): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A532): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A533): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A534): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A535),through L_(A550), each L_(A551) through L_(A566), each represented bythe formula: represented by the formula:

  wherein in L_(A535): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A536):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A537): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A538): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A539): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A540): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A541): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A542): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A543): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A544): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A545): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A546): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A547): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A548): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A549): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A550): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A551): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A552):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A553): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A554): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A555): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A556): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A557): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A558): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A559): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A560): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A561): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A562): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A563): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A564): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A565): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A566): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A567)through L_(A582), each L_(A551) through L_(A598), each represented bythe formula: represented by the formula:

  wherein in L_(A567): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A568):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A569): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A570): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A571): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A572): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A573): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A574): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A575): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A576): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A577): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A578): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A579): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A580): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A581): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A582): X=S, R^(E) = R^(A8), R² = R^(B2).,

  wherein in L_(A583): X=O, R^(E) = R^(A5), R² = R^(B1), in L_(A584):X=O, R^(E) = R^(A5), R² = R^(B2), in L_(A585): X=O, R^(E) = R^(A6), R² =R^(B1), in L_(A586): X=O, R^(E) = R^(A6), R² = R^(B2), in L_(A587): X=O,R^(E) = R^(A7), R² = R^(B1), in L_(A588): X=O, R^(E) = R^(A7), R² =R^(B2), in L_(A589): X=O, R^(E) = R^(A8), R² = R^(B1), in L_(A590): X=O,R^(E) = R^(A8), R² = R^(B2), in L_(A591): X=S, R^(E) = R^(A5), R² =R^(B1), in L_(A592): X=S, R^(E) = R^(A5), R² = R^(B2), in L_(A593): X=S,R^(E) = R^(A6), R² = R^(B1), in L_(A594): X=S, R^(E) = R^(A6), R² =R^(B2), in L_(A595): X=S, R^(E) = R^(A7), R² = R^(B1), in L_(A596): X=S,R^(E) = R^(A7), R² = R^(B2), in L_(A597): X=S, R^(E) = R^(A8), R² =R^(B1), and in L_(A598): X=S, R^(E) = R^(A8), R² = R^(B2)., L_(A599)through L_(A606), each L_(A607) through L_(A614), each represented bythe formula: represented by the formula:

  wherein in L_(A599): R^(E) = R^(A5), R¹ = R^(C1), in L_(A600): R^(E) =R^(A6), R¹ = R^(C1), in L_(A601): R^(E) = R^(A7), R¹ = R^(C1), inL_(A602): R^(E) = R^(A8), R¹ = R^(C1), in L_(A603): R^(E) = R^(A5), R¹ =R^(C2), in L_(A604): R^(E) = R^(A6), R¹ = R^(C2), in L_(A605): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A606): R^(E) = R^(A8), R¹ = R^(C2).,

  wherein in L_(A607): R^(E) = R^(A5), R¹ = R^(C1), in L_(A608): R^(E) =R^(A6), R¹ = R^(C1), in L_(A609): R^(E) = R^(A7), R¹ = R^(C1), inL_(A610): R^(E) = R^(A8), R¹ = R^(C1), in L_(A611): R^(E) = R^(A5), R¹ =R^(C2), in L_(A612): R^(E) = R^(A6), R¹ = R^(C2), in L_(A613): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A613): R^(E) = R^(A8), R¹ = R^(C2).,L_(A615) through L_(A622), each L_(A623) through L_(A630), eachrepresented by the formula: represented by the formula:

  wherein in L_(A615): R^(E) = R^(A5), R¹ = R^(C1), in L_(A616): R^(E) =R^(A6), R¹ = R^(C1), in L_(A617): R^(E) = R^(A7), R¹ = R^(C1), inL_(A618): R^(E) = R^(A8), R¹ = R^(C1), in L_(A619): R^(E) = R^(A5), R¹ =R^(C2), in L_(A620): R^(E) = R^(A6), R¹ = R^(C2), in L_(A621): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A622): R^(E) = R^(A8), R¹ = R^(C2).,

  wherein in L_(A623): R^(E) = R^(A5), R¹ = R^(C1), in L_(A624): R^(E) =R^(A6), R¹ = R^(C1), in L_(A625): R^(E) = R^(A7), R¹ = R^(C1), inL_(A626): R^(E) = R^(A8), R¹ = R^(C1), in L_(A627): R^(E) = R^(A5), R¹ =R^(C2), in L_(A628): R^(E) = R^(A6), R¹ = R^(C2), in L_(A629): R^(E) =R^(A7), R¹ = R^(C2), and in L_(A630): R^(E) = R^(A8), R¹ = R^(C2).,wherein R^(A5) to R^(A8) have thefollowing structures:

wherein R^(B1) and R^(B2) have the followingstructures:

and wherein R^(C1) to R^(C2) have the following structures:

The Triazine embodiment wherein L_(B) is selected from the groupconsisting of:

The Triazine embodiment wherein L_(C) is selected from the groupconsisting of:

In some embodiments, the compound is selected from the group consistingof Compound 1 through Compound 25,830, wherein each Compound x has theformula Ir(L_(Ak))(L_(Bj))₂, wherein x=630j+k−630, k is an integer from1 to 630, and j is an integer from 1 to 41.

In some embodiments, the compound is selected from the group consistingof Compound 25,831 through Compound 34,020, wherein each Compound x hasthe formula Ir(L_(Ak))₂(L_(Ci)), wherein x=(630i+k−630)+25,830, k is aninteger from 1 to 630, and i is an integer from 1 to 13.

According to another aspect of the present disclosure, a device thatincludes one or more organic light emitting devices is also provided. Atleast one of the one or more organic light emitting devices can includean anode, a cathode, and an organic layer disposed between the anode andthe cathode. The organic layer may include a host and a phosphorescentdopant. The emissive layer can include the compound according to FormulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z), and its variations as describedherein.

The device can be one or more of a consumer product, an electroniccomponent module, an organic light-emitting device and a lighting panel.The organic layer can be an emissive layer and the compound can be anemissive dopant in some embodiments, while the compound can be anon-emissive dopant in other embodiments.

The organic layer can also include a host. In some embodiments, the hostcan include a metal complex. The host can be a triphenylene containingbenzo-fused thiophene or benzo-fused furan. Any substituent in thetriphenylene containing benzo-fused thiophene or benzo-fused furan hostcan be an unfused substituent independently selected from the groupconsisting of CH_(2n+1), OC_(n)H_(2n+1), OAr₁, N(C_(n)H_(2n+1))₂,N(Ar₁)(Ar₂), CH≡CH—CH_(2n+1), C≡C—C_(n)H_(2n+1), Ar₁, Ar₁-Ar₂, andCH₂—Ar₁, or no substitution. In the preceding substituents, n can rangefrom 1 to 10; and Ar₁ and Ar₂ can be independently selected from thegroup consisting of benzene, biphenyl, naphthalene, triphenylene,carbazole, and heteroaromatic analogs thereof.

The host can be a compound comprising at least one chemical groupselected from the group consisting of triphenylene, carbazole,dibenzothiphene, dibenzofuran, dibenzoselenophene, azatriphenylene,azacarbazole, aza-dibenzothiophene, aza-dibenzofuran, andaza-dibenzoselenophene. The host can be a specific compound selectedfrom the group consisting of:

and combinations thereof.

In yet another aspect of the present disclosure, a formulation thatcomprises the compound according to FormulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z) is described and its variantsdescribed herein. The formulation can include one or more componentsselected from the group consisting of a solvent, a host, a holeinjection material, hole transport material, and an electron transportlayer material, disclosed herein.

Combination with Other Materials

The materials described herein as useful for a particular layer in anorganic light emitting device may be used in combination with a widevariety of other materials present in the device. For example, emissivedopants disclosed herein may be used in conjunction with a wide varietyof hosts, transport layers, blocking layers, injection layers,electrodes and other layers that may be present. The materials describedor referred to below are non-limiting examples of materials that may beuseful in combination with the compounds disclosed herein, and one ofskill in the art can readily consult the literature to identify othermaterials that may be useful in combination.

HIL/HTL:

A hole injecting/transporting material to be used in the presentinvention is not particularly limited, and any compound may be used aslong as the compound is typically used as a hole injecting/transportingmaterial. Examples of the material include, but are not limited to: aphthalocyanine or porphyrin derivative; an aromatic amine derivative; anindolocarbazole derivative; a polymer containing fluorohydrocarbon; apolymer with conductivity dopants; a conducting polymer, such asPEDOT/PSS; a self-assembly monomer derived from compounds such asphosphonic acid and silane derivatives; a metal oxide derivative, suchas MoO_(x); a p-type semiconducting organic compound, such as1,4,5,8,9,12-Hexaazatriphenylenehexacarbonitrile; a metal complex, and across-linkable compounds.

Examples of aromatic amine derivatives used in HIL or HTL include, butare not limited to, the following general structures:

Each of Ar¹ to Ar⁹ is selected from the group consisting of aromatichydrocarbon cyclic compounds such as benzene, biphenyl, triphenyl,triphenylene, naphthalene, anthracene, phenalene, phenanthrene,fluorene, pyrene, chrysene, perylene, and azulene; the group consistingof aromatic heterocyclic compounds such as dibenzothiophene,dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran,benzothiophene, benzoselenophene, carbazole, indolocarbazole,pyridylindole, pyrrolodipyridine, pyrazole, imidazole, triazole,oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole,pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine,oxathiazine, oxadiazine, indole, benzimidazole, indazole, indoxazine,benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline,cinnoline, quinazoline, quinoxaline, naphthyridine, phthalazine,pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine,benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and the group consisting of 2 to 10 cyclic structural units which aregroups of the same type or different types selected from the aromatichydrocarbon cyclic group and the aromatic heterocyclic group and arebonded to each other directly or via at least one of oxygen atom,nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom,chain structural unit and the aliphatic cyclic group. Wherein each Ar isfurther substituted by a substituent selected from the group consistingof hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof.

In one aspect, Ar¹ to Ar⁹ is independently selected from the groupconsisting of:

wherein k is an integer from 1 to 20; X¹⁰¹ to X¹⁰⁸ is C (including CH)or N; Z¹⁰¹ is NAr¹, O, or S; Ar¹ has the same group defined above.

Examples of metal complexes used in HIL or HTL include, but are notlimited to, the following general formula:

wherein Met is a metal, which can have an atomic weight greater than 40;(Y¹⁰¹-Y¹⁰²) is a bidentate ligand, Y¹⁰¹ and Y¹⁰² are independentlyselected from C, N, O, P, and S; L¹⁰¹ is an ancillary ligand; k′ is aninteger value from 1 to the maximum number of ligands that may beattached to the metal; and k′+k″ is the maximum number of ligands thatmay be attached to the metal.

In one aspect, (Y¹⁰¹-Y¹⁰²) is a 2-phenylpyridine derivative. In anotheraspect, (Y¹⁰¹-Y¹⁰²) is a carbene ligand. In another aspect, Met isselected from Ir, Pt, Os, and Zn. In a further aspect, the metal complexhas a smallest oxidation potential in solution vs. Fc⁺/Fc couple lessthan about 0.6 V.

Host:

The light emitting layer of the organic EL device of the presentinvention preferably contains at least a metal complex as light emittingmaterial, and may contain a host material using the metal complex as adopant material. Examples of the host material are not particularlylimited, and any metal complexes or organic compounds may be used aslong as the triplet energy of the host is larger than that of thedopant. While the Table below categorizes host materials as preferredfor devices that emit various colors, any host material may be used withany dopant so long as the triplet criteria is satisfied.

Examples of metal complexes used as host are preferred to have thefollowing general formula:

wherein Met is a metal; (Y¹⁰³-Y¹⁰⁴) is a bidentate ligand, Y¹⁰³ and Y¹⁰⁴are independently selected from C, N, O, P, and S; L¹⁰¹ is an anotherligand; k′ is an integer value from 1 to the maximum number of ligandsthat may be attached to the metal; and k′+k″ is the maximum number ofligands that may be attached to the metal.

In one aspect, the metal complexes are:

wherein (O—N) is a bidentate ligand, having metal coordinated to atoms Oand N.

In another aspect, Met is selected from Ir and Pt. In a further aspect,(Y¹⁰³-Y¹⁰⁴) is a carbene ligand.

Examples of organic compounds used as host are selected from the groupconsisting of aromatic hydrocarbon cyclic compounds such as benzene,biphenyl, triphenyl, triphenylene, naphthalene, anthracene, phenalene,phenanthrene, fluorene, pyrene, chrysene, perylene, and azulene; thegroup consisting of aromatic heterocyclic compounds such asdibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene,benzofuran, benzothiophene, benzoselenophene, carbazole,indolocarbazole, pyridylindole, pyrrolodipyridine, pyrazole, imidazole,triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole,thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine,oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole,indoxazine, benzoxazole, benzisoxazole, benzothiazole, quinoline,isoquinoline, cinnoline, quinazoline, quinoxaline, naphthyridine,phthalazine, pteridine, xanthene, acridine, phenazine, phenothiazine,phenoxazine, benzofuropyridine, furodipyridine, benzothienopyridine,thienodipyridine, benzoselenophenopyridine, and selenophenodipyridine;and the group consisting of 2 to 10 cyclic structural units which aregroups of the same type or different types selected from the aromatichydrocarbon cyclic group and the aromatic heterocyclic group and arebonded to each other directly or via at least one of oxygen atom,nitrogen atom, sulfur atom, silicon atom, phosphorus atom, boron atom,chain structural unit and the aliphatic cyclic group. Wherein each groupis further substituted by a substituent selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof.

In one aspect, the host compound contains at least one of the followinggroups in the molecule:

wherein R¹⁰¹ to R¹⁰⁷ is independently selected from the group consistingof hydrogen, deuterium, halide, alkyl, cycloalkyl, heteroalkyl,arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl, cycloalkenyl,heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylicacids, ester, nitrile, isonitrile, sulfanyl, sulfinyl, sulfonyl,phosphino, and combinations thereof, when it is aryl or heteroaryl, ithas the similar definition as Ar's mentioned above. k is an integer from0 to 20 or 1 to 20; k′″ is an integer from 0 to 20. X¹⁰¹ to X¹⁰⁸ isselected from C (including CH) or N. Z¹⁰¹ and Z¹⁰² is selected fromNR¹⁰¹, O, or S.HBL:

A hole blocking layer (HBL) may be used to reduce the number of holesand/or excitons that leave the emissive layer. The presence of such ablocking layer in a device may result in substantially higherefficiencies as compared to a similar device lacking a blocking layer.Also, a blocking layer may be used to confine emission to a desiredregion of an OLED.

In one aspect, compound used in HBL contains the same molecule or thesame functional groups used as host described above.

In another aspect, compound used in HBL contains at least one of thefollowing groups in the molecule:

wherein k is an integer from 1 to 20; L¹⁰¹ is an another ligand, k′ isan integer from 1 to 3.ETL:

Electron transport layer (ETL) may include a material capable oftransporting electrons. Electron transport layer may be intrinsic(undoped), or doped. Doping may be used to enhance conductivity.Examples of the ETL material are not particularly limited, and any metalcomplexes or organic compounds may be used as long as they are typicallyused to transport electrons.

In one aspect, compound used in ETL contains at least one of thefollowing groups in the molecule:

wherein R¹⁰¹ is selected from the group consisting of hydrogen,deuterium, halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy,aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl,aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile,isonitrile, sulfanyl, sulfinyl, sulfonyl, phosphino, and combinationsthereof, when it is aryl or heteroaryl, it has the similar definition asAr's mentioned above. Ar¹ to Ar³ has the similar definition as Ar'smentioned above. k is an integer from 1 to 20. X¹⁰¹ to X¹⁰⁸ is selectedfrom C (including CH) or N.

In another aspect, the metal complexes used in ETL contains, but are notlimited to, the following general formula:

wherein (O—N) or (N—N) is a bidentate ligand, having metal coordinatedto atoms O, N or N, N; L¹⁰¹ is another ligand; k′ is an integer valuefrom 1 to the maximum number of ligands that may be attached to themetal.

In any above-mentioned compounds used in each layer of the OLED device,the hydrogen atoms can be partially or fully deuterated. Thus, anyspecifically listed substituent, such as, without limitation, methyl,phenyl, pyridyl, etc. encompasses undeuterated, partially deuterated,and fully deuterated versions thereof. Similarly, classes ofsubstituents such as, without limitation, alkyl, aryl, cycloalkyl,heteroaryl, etc. also encompass undeuterated, partially deuterated, andfully deuterated versions thereof.

In addition to and/or in combination with the materials disclosedherein, many hole injection materials, hole transporting materials, hostmaterials, dopant materials, exiton/hole blocking layer materials,electron transporting and electron injecting materials may be used in anOLED. Non-limiting examples of the materials that may be used in an OLEDin combination with materials disclosed herein are listed in Table Abelow. Table A lists non-limiting classes of materials, non-limitingexamples of compounds for each class, and references that disclose thematerials.

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EXPERIMENTAL Material Synthesis

All reactions were carried out under nitrogen protections unlessspecified otherwise. All solvents for reactions are anhydrous and usedas received from commercial sources.

Synthesis of Compound 2,523 [IrL_(A3)(L_(B5))₂] Synthesis of2-bromo-9-isobutyl-9H-carbazole

2-bromo-9H-carbazole (15.0 g, 61.0 mmol) was dissolved indimethylformamide (DMF) (200 mL) under nitrogen and sodium hydride (6.70g, 170 mmol) was added in portions then stirred for 15 minutes at roomtemperature. 1-bromo-2-methylpropane (21.7 g, 160 mmol) was added to themixture via syringe and the reaction mixture was heated to 60° C. for 4hours, then left at room temperature overnight. The reaction mixture wasconcentrated down using a rotary evaporator and the residue wasextracted twice with ethyl acetate. The combined organics were washedwith brine. The crude material was purified via column chromatographyusing a heptane/ethyl acetate (90/10) solvent system to obtain 19.0 g of2-bromo-9-isobutyl-9H-carbazole as a white solid.

Synthesis of9-isobutyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

2-bromo-9-isobutyl-9H-carbazole (19.0 g, 62.9 mmol),4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (31.9 g, 130mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-3-yl)phosphine (2.07g, 5.03 mmol), potassium acetate (15.4 g, 160 mmol), and dioxane (500mL) were mixed in a flask. The mixture was degassed by bubbling withnitrogen gas for 15 minutes, then the reaction mixture was heated toreflux overnight. The reaction mixture was then filtered through Celiteand washed well with ethyl acetate to remove a gray precipitate. Thefiltrate was washed with brine, dried with sodium sulfate, and filtered,then concentrated down to an orange oil. That oil was placed on aKugelrohr and heated to 180° C. to remove the bis-pinacolate. The crudematerial was purified via column chromatography using aheptane/dichloromethane (DCM) solvent system (75/25 to 25/75) to obtain17.46 g of9-isobutyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazoleas a white solid for an 80% yield.

Synthesis of 9-isobutyl-2-(6-methyl-[2,3′-bipyridin]-6′-yl)-9H-carbazole

6′-chloro-6-methyl-2,3′-bipyridine (2.50 g, 12.2 mmol),9-isobutyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole(5.12 g, 14.7 mmol), palladium tetrakis Pd(PPh₃)₄ (0.42 g, 0.37 mmol),dimethoxyethane (DME) (80 mL), and water (20 mL) were combined in aflask. The mixture was degassed by bubbling with nitrogen gas for 15minutes, then the reaction mixture was heated to reflux overnight. Thereaction mixture was extracted with ethyl acetate and washed with water.The crude material was purified via column chromatography using aDCM/ethyl acetate solvent system (97.5/2.5 to 95/5) to afford a lightyellow solid. The product was further purified by reverse phase (C18)chromatography using acetonitrile and water (90/10) to afford 3.92 (83%yield) of 9-isobutyl-2-(6-methyl-[2,3′-bipyridin]-6′-yl)-9H-carbazole asa pale yellow solid.

Synthesis of Compound 2,523

The Ir(III) complex (1.40 g, 2.30 mmol),9-isobutyl-2-(6-methyl-[2,3′-bipyridin]-6′-yl)-9H-carbazole (2.70 g,6.89 mmol), and ethanol (50 ml) were combined and the mixture was heatedto reflux over the weekend. Upon completion of the reaction, the ethanolwas distilled under vacuum and the crude material was purified viacolumn chromatography using heptanes/DCM (75/25) to afford 1.71 g (81%yield) of pure compound 2,523.

Synthesis of Compound 26,471 [Ir(L_(A11))₂L_(C2)] Synthesis of4-chloro-2-methyl-2′-nitro-1,1′-biphenyl

1-bromo-2-nitrobenzene (20.0 g, 99 mmol),(4-chloro-2-methylphenyl)boronic acid (18.6 g, 110 mmol), potassiumcarbonate (34.2 g, 250 mmol), palladium tetrakis (3.43 g, 2.97 mmol),DME (400 ml), and water (100 ml) were combined in a round bottom flask.The mixture was degassed by bubbling with nitrogen gas for 15 minutes,then the reaction was heated to reflux overnight. Upon completion, thereaction mixture was extracted with ethyl acetate three times and theorganic layer was washed with brine twice, dried with sodium sulfate,filtered, and concentrated down to a brown oil. The crude material waspurified with silica gel using a heptane/DCM (75/25) solvent system toisolate 23.2 g (95% yield) of 4-chloro-2-methyl-2′-nitro-1,1′-biphenylas a yellow oil.

Synthesis of 2-chloro-4-methyl-9H-carbazole

4-chloro-2-methyl-2′-nitro-1,1′-biphenyl (23.2 g, 94 mmol),triphenylphosphine (73.7 g, 280 mmol), and 1,2 dichlorobenzene (450 ml)were combined in a round bottom flask. A condenser was attached, thenthe system was evacuated and purged with nitrogen three times. Thereaction mixture was heated to reflux overnight. Upon completion, thedichlorobenzene was removed by Kugelrohr at 110° C. The crude productwas purified by filtering through a silica gel plug using aheptanes/ethyl acetate (100/0 to 90/10) solvent system. The sample waspurified via column chromatography using a heptane/ethyl acetate (95/5to 90/10) solvent system to obtain 18.0 g of2-chloro-4-methyl-9H-carbazole as a beige solid for a 89% yield.

Synthesis of 2-chloro-9-isobutyl-4-methyl-9H-carbazole

2-chloro-4-methyl-9H-carbazole (9.00 g, 41.7 mmol) was dissolved in DMF(150 ml) in a round bottom flask and placed under nitrogen. Sodiumhydride (2.50 g, 62.6 mmol) was added in portions then stirred for 15minutes after addition was complete. 1-bromo-2-methylpropane (6.81 ml,62.6 mmol) was added and the reaction mixture was heated to 60° C. for 4hours, then stirred at room temperature overnight. The reaction mixturewas concentrated down on a rotovap then transferred to separatoryfunnel, extracted with ethyl acetate, and washed water. The organicswere washed once with water and twice with brine, then dried with sodiumsulfate, filtered, and concentrated down. The brown solid was purifiedvia column chromatography using Heptanes/Ethyl Acetate (95/5) solventsystem to obtain 9.1 g of 2-chloro-9-isobutyl-4-methyl-9H-carbazole as awhite solid for an 80% yield.

Synthesis of9-isobutyl-4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole

2-chloro-9-isobutyl-4-methyl-9H-carbazole (9.00 g, 33.1 mmol),4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi(1,3,2-dioxaborolane) (16.8 g,66.2 mmol), dicyclohexyl(2′,6′-dimethoxy-[1,1′-biphenyl]-3-yl)phosphine(1.09 g, 2.65 mmol), potassium acetate (8.12 g, 83.0 mmol), and dioxane(200 mL) were combined in a round bottom flask. The mixture was degassedby bubbling with nitrogen gas for 15 minutes, then the reaction mixturewas heated to reflux overnight. The reaction mixture was then filteredthrough a Celite plug and washed with ethyl acetate. The filtrate waswashed twice with brine, dried with sodium sulfate, filtered, and thenconcentrated down. The oil was purified using a Kugelrohr apparatus at180° C. to remove the bis-pinacolate. The dark brown solid was dissolvedin DCM, filtered through a Celite plug then concentrated down. The brownsolid was purified via column chromatography using heptane/DCM (75/25 to25/75) solvent system to obtain 10.3 g of9-isobutyl-4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazoleas a white solid for an 86% yield.

Synthesis of9-isobutyl-4-methyl-2-(6-methyl-[2,3′-bipyridin]-6′-yl)-9H-carbazole

6′-chloro-6-methyl-2,3′-bipyridine (3.20 g, 15.6 mmol),9-isobutyl-4-methyl-2-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole(6.25 g, 17.2 mmol), palladium tetrakis (0.542 g, 0.469 mmol), DME (120mL) and water (30 mL) were combined in a round bottom flask. The mixturewas degassed by bubbling nitrogen gas for 15 minutes and the reactionwas heated to reflux overnight. Upon completion, the reaction wasextracted using ethyl acetate, washed with water and Brine, dried withsodium sulfate, filtered through Celite then concentrated down to anorange oil. The crude material was purified via column chromatographyusing a DCM/ethyl acetate (100/0 to 85/15) solvent system. The isolatedproduct was further purified by reverse phase chromatography using anacetonitrile/water (85/15 to 100/0) solvent system to isolate 4.2 g (66%yield) of9-isobutyl-4-methyl-2-(6-methyl-[2,3′-bipyridin]-6′-yl)-9H-carbazole asan off white solid.

Synthesis of the Ir(III) Dimer

9-isobutyl-4-methyl-2-(6-methyl-[2,3′-bipyridin]-6′-yl)-9H-carbazole(4.23 g, 10.4 mmol) was placed in a round bottom flask (RBF) andsolubilized in ethoxythanol (35 mL) and water (12 mL). The mixture wasdegassed by bubbling with nitrogen gas for 15 minutes and then iridiumchloride (1.03 g, 2.78 mmol) was added and the reaction mixture washeated at 105° C. for 24 hours. The reaction mixture was cooled down toroom temperature, diluted with 10 mL of MeOH, filtered and washed withMeOH. The Ir(III) Dimer (3.2 g, 111% yield) was isolated.

Synthesis of Compound 26,471

The Ir(III) Dimer (1.60 g, 0.77 mmol), 3,7-diethylnonane-4,6-dione (1.64g, 7.72 mmol), and 2-ethoxyethanol (25 ml) were combined and the mixturewas degassed by bubbling with nitrogen gas for 15 minutes. Potassiumcarbonate (1.07 g, 7.72 mmol) was added and the reaction mixture wasstirred at room temperature overnight. Upon completion, the reactionmixture was filtered through Celite and washed with DCM. The red productwas triturated in heptanes and the red solid was purified via columnchromatography (pretreated with triethylamine) using a heptanes/DCM(90/10 to 50/50) solvent system. The combined fraction was concentrateddown and the red solid was triturated from methanol to yield 0.65 g (36%yield) of compound 26,471 as a red solid.

Synthesis of Compound 2,740 [IrL_(A220)(L_(B5))₂] Synthesis of Compound2,740

The Ir(III) complex (1.20 g, 1.61 mmol) and8-(5-(4,6-diisopropyl-1,3,5-triazin-2-yl)pyridin-2-yl)-2-methylbenzofuro[2,3-b]pyridine(2.05 g, 4.84 mmol) were mixed in Ethanol (32 mL). The reaction washeated to reflux overnight. Upon completion of the reaction, orangesolid precipitated out of the (mixture. The reaction was filtered over apad of Celite and washed with methanol until the wash was clear. Thefiltering flask was then changed and the solids on the Celite werewashed with Dichloromethane until the wash was colorless. The crudeproduct was purified via column chromatography using Heptanes/EthylAcetate 60/40) solvent system. The collected fractions were combined andthe orange product was triturated from Methanol to afford the pureemitter (1.20 g, 78% yield).

Synthesis of Compound 21,010 [IrL_(A220)(L_(B34))₂] Synthesis ofCompound 21,010

Ir(III) complex (0.90 g, 1.13 mmol) and8-(5-(4,6-diisopropyl-1,3,5-triazin-2-yl)pyridin-2-yl)-2-methylbenzofuro[2,3-b]pyridine(1.43 g, 3.38 mmol) were mixed in Ethanol (23 mL). The reaction washeated to gentle reflux overnight. Upon completion of the reaction,orange solid precipitated out of the mixture. The reaction was filteredover a pad of Celite and washed with methanol until the wash was clear.The filtering flask was then changed and the solids on the Celite werewashed with Dichloromethane until the wash was colorless. The crudeproduct was purified via column chromatography using DCM/Ethyl Acetate(100/0 to 98/2) solvent system. The collected fractions were combinedand the orange product was triturated from Methanol to afford the puredopant (0.48 g, 42% yield).

Device Examples

All example devices were fabricated by high vacuum (<10⁻⁷ Torr) thermalevaporation. The anode electrode was 1200 Å of indium tin oxide (ITO).The cathode consisted of 10 Å of LiF followed by 1,000 Å of Al. Alldevices were encapsulated with a glass lid sealed with an epoxy resin ina nitrogen glove box (<1 ppm of H₂O and O₂) immediately afterfabrication, and a moisture getter was incorporated inside the package.The organic stack of the device examples consisted of sequentially, fromthe ITO surface, 100 Å of LG101 (purchased from LG chem) as the holeinjection layer (HIL); 400 Å of4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPD) as the holetransporting layer (HTL); 300 Å of an emissive layer (EML) containingCompound H as a host (79%), a stability dopant (SD) (18%), and Compound401 or Compound 24 as an emitter; 100 Å of Compound H as a blockinglayer; and 450 Å of Alq₃ (tris-8-hydroxyquinoline aluminum) as the ETL.The emitter was selected to provide the desired color and the stabilitydopant (SD) was mixed with the electron-transporting host and theemitter to help transport positive charge in the emissive layer. Table 1shows the composition of the EML in the device, while the device resultsand data are summarized in Table 2.

As used herein, NPD, compound H, SD, and AlQ₃ have the followingstructures:

Table 1. Compounds of EML in the Devices

Example Emitter Device Compound 2,523 Example 1 Device Compound 26,471Example 2 Device Compound 2,740 Example 3 Device Compound 21,010 Example4

TABLE 2 Device results of Device examples 1 and 2. EQE at LT_(95%) at1931 CIE λ max FWHM 1,000 nits 1,000 nits x y [nm] [nm] [%] [hours]Device 0.63 0.36 614 81 17.0 5,500 Example 1 Device 0.69 0.31 652 7011.0 1,000 Example 2 Device 0.59 0.41 600 74 18.7 16,600 Example 3Device 0.60 0.40 606 81 18.1 12,700 Example 4

Table 2 summarizes the performance of the devices. The 1931 CIE valueswere measured at 10 mA/cm². The luminous efficiency and the lifetime(LT_(95%)) were measured at 1000 cd/m². The device examples show thatcombining L_(A) with either L_(B) or L_(C) changes the deviceproperties. L_(B) combined with L_(A) tends to provide dopants withbroader emission. The broad FWHM is useful for lighting applications. Onthe other hand, the emission spectrum from dopant based on thecombination of L_(A) and L_(C) is narrower which helps to provide abetter color quality. Therefore, iridium complexes described in thisinvention provide a broad range of useful materials for both lightingand display applications.

It is understood that the various embodiments described herein are byway of example only, and are not intended to limit the scope of theinvention. For example, many of the materials and structures describedherein may be substituted with other materials and structures withoutdeviating from the spirit of the invention. The present invention asclaimed may therefore include variations from the particular examplesand preferred embodiments described herein, as will be apparent to oneof skill in the art. It is understood that various theories as to whythe invention works are not intended to be limiting.

We claim:
 1. A compound having a formulaM(L_(A))_(x)(L_(B))_(y)(L_(C))_(z): wherein the ligand L_(A) is

wherein the ligand L_(B) is

wherein the ligand L_(C) is

wherein M is a metal having an atomic number greater than 40; wherein xis 1, or 2; wherein y is 0, 1, or 2; wherein z is 0, 1, or 2; whereinx+y+z is the oxidation state of the metal M; wherein A¹, A², A³, A⁴, A⁵,A⁶, A⁷, and A⁸ are carbon or nitrogen; wherein ring B is bonded to ringA through a C—C bond; wherein M is bonded to ring A through an M-C bond;wherein X is selected from the group consisting of O, S, Se, CRR′, andNR¹; wherein rings C and D are each independently a 5 or 6-memberedcarbocyclic or heterocyclic ring; wherein R³ represents mono, ordi-substitution, or no substitution; wherein R², R^(C), and R^(D) eachindependently represent mono, di, tri, or tetra-substitution, or nosubstitution; wherein R⁴ represents mono, di, tri, ortetra-substitution; wherein at least one R⁴ is a triazine ring which isfurther substituted by R^(E); wherein R^(E) represents mono ordi-substitution; wherein each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D),R^(X), R^(Y), R^(Z), and R^(E) are independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; wherein at least oneR^(E) is selected from the group consisting of alkyl, cycloalkyl,heteroalkyl, arylalkyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, sulfanyl, sulfinyl, sulfonyl, phosphino,partially or fully deuterated variations thereof, and combinationsthereof; wherein any adjacent substitutents of R, R′, R¹, R², R³, R⁴,R^(C), R^(D), R^(X), R^(Y), R^(Z), and R^(E) are optionally joined toform a ring; and at least one of the following is true: (i) at least oneR^(E) is selected from the group consisting of alkyl, cycloalkyl,partially or fully deuterated variations thereof, partially or fullyfluorinated variations thereof, and combinations thereof, and (ii)exactly one of A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ is nitrogen.
 2. Thecompound of claim 1, wherein M is selected from the group consisting ofIr, Rh, Re, Ru, Os, Pt, Au, and Cu.
 3. The compound of claim 1, whereinthe compound has the formula M(L_(A))₂(L_(C)).
 4. The compound of claim1, wherein the compound has the formula M(L_(A))(L_(B))₂.
 5. Thecompound of claim 1, wherein A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ arecarbon.
 6. The compound of claim 1, wherein exactly one of A¹, A², A³,A⁴, A⁵, A⁶, A⁷, and A⁸ is nitrogen.
 7. The compound of claim 1, whereinX is O or NR¹.
 8. The compound of claim 1, wherein ring C is benzene,and ring D is pyridine.
 9. The compound of claim 1, wherein L_(A) isselected from the group consisting of:


10. The compound of claim 1, wherein L_(B) is selected from the groupconsisting of:


11. The compound of claim 1, where L_(C) is selected from the groupconsisting of:


12. The compound of claim 1, wherein R^(E) is di-substituted.
 13. Thecompound of claim 1, wherein L_(A) is selected from the group consistingof: L_(A185) through L_(A190) and L_(A193) through L_(A198), eachrepresented by the formula:

wherein in L_(A185): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A186) : X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A187): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A188): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A189):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A190): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A193): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A194): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A195): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A196): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A197): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A198): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A201) through L_(A206) and L_(A209)through L_(A214), each represented by the formula:

wherein in L_(A201): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A202): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A203): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A204): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A205):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A206): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A209): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A210): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A211): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A212): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A213): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A214): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A217) through L_(A222) and L_(A225)through L_(A230), each represented by the formula:

wherein in L_(A217): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A218): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A219): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A220): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A221):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A222): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A225): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A226): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A227): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A228): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A229): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A230): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A233) through L_(A238) and L_(A241)through L_(A246), each represented by the formula:

wherein in L_(A233): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A234): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A235): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A236): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A237):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A238): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A241): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A242): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A243): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A244): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A245): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A246): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A249) through L_(A254) and L_(A257)through L_(A262), each represented by the formula:

wherein in L_(A249): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A250): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A251): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A252): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A253):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A254): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A257): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A258): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A259): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A260): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A261): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A262): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A265) through L_(A270) and L_(A273)through L_(A278), each represented by the formula:

wherein in L_(A265): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A266): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A267): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A268): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A269):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A270): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A273): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A274): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A275): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A276): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A277): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A278): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A281) through L_(A286) and L_(A289)through L_(A294), each represented by the formula:

wherein in L_(A281): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A282): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A283): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A284): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A285):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A286): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A289): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A290): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A291): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A292): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A293): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A294): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A297) through L_(A302) and L_(A306)through L_(A310), each represented by the formula:

wherein in L_(A297): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A298): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A299): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A300): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A301):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A302): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A305): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A306): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A307): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A308): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A309): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A310): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A313) through L_(A318) and L_(A321)through L_(A326), each represented by the formula:

wherein in L_(A313): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C1), inL_(A314): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C1), in L_(A315): R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C1), in L_(A316): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C1), in L_(A317): R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C1), in L_(A318): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C1), inL_(A321): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), in L_(A322): R^(E) =R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A323): R^(E) = R^(A7), R² =R^(B1), R¹ = R^(C2), in L_(A324) : R^(E) = R^(A7), R² = R^(B2), R¹ =R^(C2), in L_(A325): R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C2), and inL_(A326): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2), L_(A329) throughL_(A334) and L_(A337) through L_(A342), each represented by the formula:

wherein in L_(A329): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C1), inL_(A330): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C1), in L_(A331): R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C1), in L_(A332): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C1), in L_(A333): R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C1), in L_(A334): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C1), inL_(A337): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), in L_(A338): R^(E) =R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A339): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C2), in L_(A340): R^(E) = R^(A7), R² = R^(B2), R¹ =R^(C2), in L_(A341): R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C2), and inL_(A342): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2), L_(A345) throughL_(A350) and L_(A353) through L_(A358), each represented by the formula:

wherein in L_(A345): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C1), inL_(A346): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C1), in L_(A347): R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C1), in L_(A348): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C1), in L_(A349): R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C1), in L_(A350): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C1), inL_(A353): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), in L_(A354): R^(E) =R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A355): R^(E) = R^(A7), R² =R^(B1), R¹ = R^(C2), in L_(A356): R^(E) = R^(A7), R² = R^(B2), R¹ =R^(C2), in L_(A357): R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C2), and inL_(A358): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2), L_(A361) throughL_(A366) and L_(A369) through L_(A374), each represented by the formula:

wherein in L_(A361): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C1), inL_(A362): R^(E) = R^(A6), R² = R^(B2), R¹ = R^(C1), in L_(A363): R^(E) =R^(A7), R² = R^(B1), R¹ = R^(C1), in L_(A364): R^(E) = R^(A7), R² =R^(B2), R¹ = R^(C1), in L_(A365): R^(E) = R^(A8), R² = R^(B1), R¹ =R^(C1), in L_(A366): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C1), inL_(A369): R^(E) = R^(A6), R² = R^(B1), R¹ = R^(C2), in L_(A370): R^(E) =R^(A6), R² = R^(B2), R¹ = R^(C2), in L_(A371): R^(E) = R^(A7), R² =R^(B1), R¹ = R^(C2), in L_(A372): R^(E) = R^(A7), R² = R^(B2), R¹ =R^(C2), in L_(A373): R^(E) = R^(A8), R² = R^(B1), R¹ = R^(C2), and inL_(A374): R^(E) = R^(A8), R² = R^(B2), R¹ = R^(C2), L_(A376) throughL_(A378) and L_(A380) through L_(A382), each represented by the formula:

wherein in L_(A376): X = O, R^(E) = R^(A6), in L_(A377): X = O, R^(E) =R^(A7), in L_(A378): X = O, R^(E) = R^(A8), in L_(A380): X = S, R^(E) =R^(A6), in L_(A381): X = S, R^(E) = R^(A7), and in L_(A382): X = S,R^(E) = R^(A8), L_(A384) through L_(A386) and L_(A388) through L_(A390),each represented by the formula::

wherein in L_(A384): X = O, R^(E) = R^(A6), in L_(A385): X = O, R^(E) =R^(A7), in L_(A386): X = O, R^(E) = R^(A8), in L_(A388): X = S, R^(E) =R^(A8), in L_(A389): X = S, R^(E) = R^(A7), and in L_(A390): X = S,R^(E) = R^(A8), L_(A393) through L_(A398) and L_(A401) through L_(A406),each represented by the formula:

wherein in L_(A393): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A394): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A395): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A396): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A397):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A398): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A401): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A402): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A403): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A404): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A405): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A406): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A409) through L_(A414) and L_(A417)through L_(A422), each represented by the formula:

wherein in L_(A409): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A410): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A411): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A412): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A413):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A414): X = O, R^(E) = R^(A6),R² = R^(B2), in L_(A417): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A418): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A419): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A420): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A421): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A422): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A425) through L_(A430) and L_(A433)through L_(A438), each represented by the formula:

wherein in L_(A425): X = O, R^(E) = R^(A6), R⁴ = R^(B1), in L_(A426): X= O, R^(E) = R^(A6), R⁴ = R^(B2), in L_(A427): X = O, R^(E) = R^(A7), R⁴= R^(B1), in L_(A428): X = O, R^(E) = R^(A7), R⁴ = R^(B2), in L_(A429):X = O, R^(E) = R^(A8), R⁴ = R^(B1), in L_(A430): X = O, R^(E) = R^(A8),R⁴ = R^(B2), in L_(A433): X = S, R^(E) = R^(A6), R⁴ = R^(B1), inL_(A434): X = S, R^(E) = R^(A6), R⁴ = R^(B2), in L_(A435): X = S, R^(E)= R^(A7), R⁴ = R^(B1), in L_(A436): X = S, R^(E) = R^(A7), R⁴ = R^(B2),in L_(A437): X = S, R^(E) = R^(A8), R⁴ = R^(B1), and in L_(A438): X = S,R^(E) = R^(A8), R⁴ = R^(B2), L_(A441) through L_(A446) and L_(A449)through L_(A454), each represented by the formula:

wherein in L_(A441): X = O, R^(E) = R^(A6), R⁴ = R^(B1), in L_(A442): X= O, R^(E) = R^(A6), R⁴ = R^(B2), in L_(A443): X = O, R^(E) = R^(A7), R⁴= R^(B1), in L_(A444): X = O, R^(E) = R^(A7), R⁴ = R^(B2), in L_(A445):X = O, R^(E) = R^(A8), R⁴ = R^(B1), in L_(A446): X = O, R^(E) = R^(A8),R⁴ = R^(B2), in L_(A449): X = S, R^(E) = R^(A6), R⁴ = R^(B1), inL_(A450): X = S, R^(E) = R^(A6), R⁴ = R^(B2), in L_(A451): X = S, R^(E)= R^(A7), R⁴ = R^(B1), in L_(A452): X = S, R^(E) = R^(A7), R⁴ = R^(B2),in L_(A453): X = S, R^(E) = R^(A8), R⁴ = R^(B1), and in L_(A454): X = S,R^(E) = R^(A8), R⁴ = R^(B2), L_(A456) through L_(A458) and L_(A460)through L_(A462), each represented by the formula:

wherein in L_(A456): X = O, R^(E) = R^(A6), in L_(A457): X = O, R^(E) =R^(A7), in L_(A458): X = O, R^(E) = R^(A8), in L_(A460): X = S, R^(E) =R^(A6), in L_(A461): X = S, R^(E) = R^(A7), and in L_(A462): X = S,R^(E) = R^(A8), L_(A464) through L_(A466) and L_(A468) through L_(A470),each represented by the formula:

wherein in L_(A464): X = O, R^(E) = R^(A6), in L_(A465): X = O, R^(E) =R^(A7), in L_(A466): X = O, R^(E) = R^(A8), in L_(A468) : X = S, R^(E) =R^(A6), in L_(A469): X = S, R^(E) = R^(A7), and in L_(A470) : X = S,R^(E) = R^(A8), L_(A472) through L_(A474) and L_(A476) through L_(A478),each represented by the formula:

wherein in L_(A472): R^(E) = R^(A6), R¹ = R^(C1), in L_(A473): R^(E) =R^(A7), R¹ = R^(C1), in L_(A474): R^(E) = R^(A8), R¹ = R^(C1), inL_(A476): R^(E) = R^(A6), R¹ = R^(C2), in L_(A477): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A478): R^(E) = R^(A8), R¹ = R^(C2), L_(A480) throughL_(A482) and L_(A484) through L_(A486), each represented by the formula:

wherein in L_(A480): R^(E) = R^(A6), R¹ = R^(C1), in L_(A481): R^(E) =R^(A7), R¹ = R^(C1), in L_(A482): R^(E) = R^(A8), R¹ = R^(C1), inL_(A484): R^(E) = R^(A6), R¹ = R^(C2), in L_(A485): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A486): R^(E) = R^(A8), R¹ = R^(C2), L_(A488) throughL_(A490) and L_(A492) through L_(A494), each represented by the formula:

wherein in L_(A488): R^(E) = R^(A6), R¹ = R^(C1), in L_(A489): R^(E) =R^(A7), R¹ = R^(C1), in L_(A490): R^(E) = R^(A8), R¹ = R^(C1), inL_(A492): R^(E) = R^(A6), R¹ = R^(C2), in L_(A493): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A494): R^(E) = R^(A8), R¹ = R^(C2), L_(A496) throughL_(A498) and L_(A500) through L_(A502), each represented by the formula:

wherein in L_(A496): R^(E) = R^(A6), R¹ = R^(C1), in L_(A497): R^(E) =R^(A7), R¹ = R^(C1), in L_(A498): R^(E) = R^(A8), R¹ = R^(C1), inL_(A500): R^(E) = R^(A6), R¹ = R^(C2), in L_(A501): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A502): R^(E) = R^(A8), R¹ = R^(C2), L_(A505) throughL_(A510) and L_(A513) through L_(A518), each represented by the formula:

wherein in L_(A505): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A506): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A507): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A508): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A509):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A510): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A513): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A514): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A515): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A516): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A517): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A518): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A521) through L_(A526) and L_(A529)through L_(A534), each represented by the formula:

wherein in L_(A521): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A522) : X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A523): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A524) : X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A525):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A526): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A529): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A530): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A531): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A532): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A533): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A534): X = SR^(E) = R^(A8), R² = R^(B2), L_(A537) through L_(A542) and L_(A545)through L_(A550), each represented by the formula:

wherein in L_(A537): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A538): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A539): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A540): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A541):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A542): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A545): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A546): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A547): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A548): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A549): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A550): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A553) through L_(A558) and L_(A561)through L_(A566), each represented by the formula:

wherein in L_(A553): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A554): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A555): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A556): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A557):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A558): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A561): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A562): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A563): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A564): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A565): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A566): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A569) through L_(A574) and L_(A577)through L_(A582), each represented by the formula:

wherein in L_(A569): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A570): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A571): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A572): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A573):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A574): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A577): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A578): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A579): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A580): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A581): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A582): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A585) through L_(A590) and L_(A593)through L_(A598), each represented by the formula:

wherein in L_(A585): X = O, R^(E) = R^(A6), R² = R^(B1), in L_(A586): X= O, R^(E) = R^(A6), R² = R^(B2), in L_(A587): X = O, R^(E) = R^(A7), R²= R^(B1), in L_(A588): X = O, R^(E) = R^(A7), R² = R^(B2), in L_(A589):X = O, R^(E) = R^(A8), R² = R^(B1), in L_(A590): X = O, R^(E) = R^(A8),R² = R^(B2), in L_(A593): X = S, R^(E) = R^(A6), R² = R^(B1), inL_(A594): X = S, R^(E) = R^(A6), R² = R^(B2), in L_(A595): X = S, R^(E)= R^(A7), R² = R^(B1), in L_(A596): X = S, R^(E) = R^(A7), R² = R^(B2),in L_(A597): X = S, R^(E) = R^(A8), R² = R^(B1), and in L_(A598): X = S,R^(E) = R^(A8), R² = R^(B2), L_(A600) through L_(A602) and L_(A604)through L_(A606), each represented by the formula:

wherein in L_(A600): R^(E) = R^(A6), R¹ = R^(C1), in L_(A601): R^(E) =R^(A7), R¹ = R^(C1), in L_(A602): R^(E) = R^(A8), R¹ = R^(C1), inL_(A604): R^(E) = R^(A6), R¹ = R^(C2), in L_(A605): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A606): R^(E) = R^(A8), R¹ = R^(C2), L_(A608) throughL_(A610) and L_(A612) through L_(A614), each represented by the formula:

wherein in L_(A608): R^(E) = R^(A6), R¹ = R^(C1), in L_(A609): R^(E) =R^(A7), R¹ = R^(C1), in L_(A610): R^(E) = R^(A8), R¹ = R^(C1), inL_(A612): R^(E) = R^(A6), R¹ = R^(C2), in L_(A613): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A614): R^(E) = R^(A8), R¹ = R^(C2), L_(A616) throughL_(A618) and L_(A620) through L_(A622), each represented by the formula:

wherein in L_(A616): R^(E) = R^(A6), R¹ = R^(C1), in L_(A617): R^(E) =R^(A7), R¹ = R^(C1), in L_(A618): R^(E) = R^(A8), R¹ = R^(C1), inL_(A620): R^(E) = R^(A6), R¹ = R^(C2), in L_(A621): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A622): R^(E) = R^(A8), R¹ = R^(C2), and L_(A624)through L_(A626) and L_(A628) through L_(A630), each represented by theformula:

wherein in L_(A624): R^(E) = R^(A6), R¹ = R^(C1), in L_(A625): R^(E) =R^(A7), R¹ = R^(C1), in L_(A626): R^(E) = R^(A8), R¹ = R^(C1), inL_(A628): R^(E) = R^(A6), R¹ = R^(C2), in L_(A629): R^(E) = R^(A7), R¹ =R^(C2), and in L_(A630) = R^(E) = R^(A8), R1= R^(C2),

wherein R^(A6) to R^(A8) have the following structures:

wherein R^(B1) and R^(B2) have the following structures:

and wherein R^(C1) to R^(C2) have the following structures:


14. The compound of claim 13, wherein the compound has the formulaIr(L_(Ak))(L_(Bj))₂; wherein L_(Ak) is selected from L_(A185)-L_(A190),L_(A193)-L_(A198), L_(A201)-L_(A206), L_(A209)-L_(A214),L_(A217)-L_(A222), L_(A225)-L_(A230), L_(A233)-L_(A238),L_(A241)-L_(A246), L_(A249)-L_(A254), L_(A257)-L_(A262),L_(A265)-L_(A270), L_(A273)-L_(A278), L_(A281)-L_(A286),L_(A289)-L_(A294), L_(A297)-L_(A302), L_(A305)-L_(A310),L_(A313)-L_(A318), L_(A321)-L_(A326), L_(A329)-L_(A334),L_(A337)-L_(A342), L_(A345)-L_(A350), L_(A353)-L_(A358),L_(A361)-L_(A366), L_(A369)-L_(A374), L_(A376)-L_(A378),L_(A380)-L_(A382), L_(A384)-L_(A386), L_(A388)-L_(A390),L_(A393)-L_(A398), L_(A401)-L_(A408), L_(A411)-L_(A414),L_(A417)-L_(A422), L_(A425)-L_(A430), L_(A433)-L_(A438),L_(A441)-L_(A446), L_(A449)-L_(A454), L_(A456)-L_(A458),L_(A460)-L_(A462), L_(A464)-L_(A466), L_(A468)-L_(A470),L_(A472)-L_(A474), L_(A476)-L_(A478), L_(A480)-L_(A482),L_(A484)-L_(A486), L_(A488)-L_(A490), L_(A492)-L_(A494),L_(A496)-L_(A498), L_(A500)-L_(A502), L_(A505)-L_(A510),L_(A513)-L_(A518), L_(A521)-L_(A526), L_(A529)-L_(A534),L_(A534)-L_(A542), L_(A545)-L_(A550), L_(A553)-L_(A558),L_(A561)-L_(A566), L_(A569)-L_(A574), L_(A577)-L_(A582),L_(A585)-L_(A590), L_(A593)-L_(A598), L_(A600)-L_(A602),L_(A604)-L_(A606), L_(A608)-L_(A610), L_(A612)-L_(A614),L_(A616)-L_(A618), L_(A620)-L_(A622), L_(A624)-L_(A626), andL_(A628)-L_(A630); and wherein L_(Bj) is selected from L_(B1) throughL_(B41) are defined as follows:


15. The compound of claim 13, wherein the compound has the formulaIr(L_(Ak))₂(L_(Ci)); wherein L_(Ak) is selected from L_(A185)-L_(A190),L_(A193)-L_(A198), L_(A201)-L_(A206), L_(A209)-L_(A214),L_(A217)-L_(A222), L_(A225)-L_(A230), L_(A233)-L_(A238),L_(A241)-L_(A246), L_(A249)-L_(A254), L_(A257)-L_(A262),L_(A265)-L_(A270), L_(A273)-L_(A278), L_(A281)-L_(A286),L_(A289)-L_(A294), L_(A297)-L_(A302), L_(A305)-L_(A310),L_(A313)-L_(A318), L_(A321)-L_(A326), L_(A329)-L_(A334),L_(A337)-L_(A342), L_(A345)-L_(A350), L_(A353)-L_(A358),L_(A361)-L_(A366), L_(A369)-L_(A374), L_(A376)-L_(A378),L_(A380)-L_(A382), L_(A384)-L_(A386), L_(A388)-L_(A390),L_(A393)-L_(A398), L_(A401)-L_(A408), L_(A411)-L_(A414),L_(A417)-L_(A422), L_(A425)-L_(A430), L_(A433)-L_(A438),L_(A441)-L_(A446), L_(A449)-L_(A454), L_(A456)-L_(A458),L_(A460)-L_(A462), L_(A464)-L_(A466), L_(A468)-L_(A470),L_(A472)-L_(A474), L_(A476)-L_(A478), L_(A480)-L_(A482),L_(A484)-L_(A486), L_(A488)-L_(A490), L_(A492)-L_(A494),L_(A496)-L_(A498), L_(A500)-L_(A502), L_(A505)-L_(A510),L_(A513)-L_(A518), L_(A521)-L_(A526), L_(A529)-L_(A534),L_(A534)-L_(A542), L_(A545)-L_(A550), L_(A553)-L_(A558),L_(A561)-L_(A566), L_(A569)-L_(A574), L_(A577)-L_(A582),L_(A585)-L_(A590), L_(A593)-L_(A598), L_(A600)-L_(A602),L_(A604)-L_(A606), L_(A608)-L_(A610), L_(A612)-L_(A614),L_(A616)-L_(A618), L_(A620)-L_(A622), L_(A624)-L_(A626), andL_(A628)-L_(A630); and wherein L_(Ci) is selected from L_(C1) throughL_(C13) are defined as follows:


16. The compound of claim 1, wherein each R^(E) is independentlyselected from the group consisting of alkyl, cycloalkyl, partially andfully deuterated variations thereof, partially or fully fluorinatedvariations thereof, and combinations thereof.
 17. A device comprisingone or more organic light emitting devices, at least one of the one ormore organic light emitting devices comprising: an anode; a cathode; andan organic layer, disposed between the anode and the cathode, comprisinga compound having a formula M(L_(A))_(x)(L_(B))_(y)(L_(C))_(z): whereinthe ligand L_(A) is

wherein the ligand L_(B) is

wherein the ligand L_(C) is

wherein M is a metal having an atomic number greater than 40; wherein xis 1, or 2; wherein y is 0, 1, or 2; wherein z is 0, 1, or 2; whereinx+y+z is the oxidation state of the metal M; wherein A¹, A², A³, A⁴, A⁵,A⁶, A⁷, and A⁸ are carbon or nitrogen; wherein ring B is bonded to ringA through a C—C bond; wherein M is bonded to ring A through an M-C bond;wherein X is selected from the group consisting of O, S, Se, CRR′, andNR¹; wherein rings C and D are each independently a 5 or 6-memberedcarbocyclic or heterocyclic ring; wherein R³ represents mono, ordi-substitution, or no substitution; wherein R², R^(C), and R^(D) eachindependently represent mono, di, tri, or tetra-substitution, or nosubstitution; wherein R⁴ represents mono, di, tri, ortetra-substitution; wherein at least one R⁴ is a triazine ring which isfurther substituted by R^(E); wherein R^(E) represents mono ordi-substitution; wherein each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D),R^(X), R^(Y), R^(Z), and R^(E) are independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; wherein at least oneR^(E) is selected from the group consisting of alkyl, cycloalkyl,heteroalkyl, arylalkyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, sulfanyl, sulfinyl, sulfonyl, phosphino,partially or fully deuterated variations thereof, and combinationsthereof; wherein any adjacent substitutents of R, R′, R¹, R², R³, R⁴,R^(C), R^(D), R^(X), R^(Y), R^(Z), and R^(E) are optionally joined toform a ring; and at least one of the following is true: (i) at least oneR^(E) is selected from the group consisting of alkyl, cycloalkyl,partially or fully deuterated variations thereof, partially or fullyfluorinated variations thereof, and combinations thereof, and (ii)exactly one of A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ is nitrogen.
 18. Thedevice of claim 17, wherein the device is selected from the groupconsisting of a consumer product, an electronic component module, anorganic light-emitting device, and a lighting panel.
 19. The device ofclaim 17, wherein the organic layer is an emissive layer and thecompound is an emissive dopant or a non-emissive dopant.
 20. The deviceof claim 17, wherein the organic layer further comprises a host, whereinthe host comprises at least one chemical group selected from the groupconsisting of triphenylene, carbazole, dibenzothiophene, dibenzofuran,dibenzoselenophene, azatriphenylene, azacarbazole, aza-dibenzothiophene,aza-dibenzofuran, and aza-dibenzoselenophene.
 21. The device of claim17, wherein the organic layer further comprises a host and the host isselected from the group consisting of:

and combinations thereof.
 22. A formulation comprising a compound havinga formula M(L_(A))_(x)(L_(B))_(y)(L_(C))_(z): wherein the ligand L_(A)is

wherein the ligand L_(B) is

wherein the ligand L_(C) is

wherein M is a metal having an atomic number greater than 40; wherein xis 1, or 2; wherein y is 0, 1, or 2; wherein z is 0, 1, or 2; whereinx+y+z is the oxidation state of the metal M; wherein A¹, A², A³, A⁴, A⁵,A⁶, A⁷, and A⁸ are carbon or nitrogen; wherein ring B is bonded to ringA through a C—C bond; wherein M is bonded to ring A through an M-C bond;wherein X is selected from the group consisting of O, S, Se, CRR′, andNR¹; wherein rings C and D are each independently a 5 or 6-memberedcarbocyclic or heterocyclic ring; wherein R³ represents mono, ordi-substitution, or no substitution; wherein R², R^(C), and R^(D) eachindependently represent mono, di, tri, or tetra-substitution, or nosubstitution; wherein R⁴ represents mono, di, tri, ortetra-substitution; wherein at least one R⁴ is a triazine ring which isfurther substituted by R^(E); wherein R^(E) represents mono ordi-substitution; wherein each of R, R′, R¹, R², R³, R⁴, R^(C), R^(D),R^(X), R^(Y), R^(Z), and R^(E) are independently selected from the groupconsisting of hydrogen, deuterium, halide, alkyl, cycloalkyl,heteroalkyl, arylalkyl, alkoxy, aryloxy, amino, silyl, alkenyl,cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl,carboxylic acids, ester, nitrile, isonitrile, sulfanyl, sulfinyl,sulfonyl, phosphino, and combinations thereof; wherein at least oneR^(E) is selected from the group consisting of alkyl, cycloalkyl,heteroalkyl, arylalkyl, silyl, alkenyl, cycloalkenyl, heteroalkenyl,alkynyl, aryl, heteroaryl, sulfanyl, sulfinyl, sulfonyl, phosphino,partially or fully deuterated variations thereof, and combinationsthereof; wherein any adjacent substitutents of R, R′, R¹, R², R³, R⁴,R^(C), R^(D), R^(X), R^(Y), R^(Z), and R^(E) are optionally joined toform a ring; and at least one of the following is true: (i) at least oneR^(E) is selected from the group consisting of alkyl, cycloalkyl,partially or fully deuterated variations thereof, partially or fullyfluorinated variations thereof, and combinations thereof, and (ii)exactly one of A¹, A², A³, A⁴, A⁵, A⁶, A⁷, and A⁸ is nitrogen.